CN101970572A - Photocurable composition - Google Patents

Photocurable composition Download PDF

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Publication number
CN101970572A
CN101970572A CN2008801025865A CN200880102586A CN101970572A CN 101970572 A CN101970572 A CN 101970572A CN 2008801025865 A CN2008801025865 A CN 2008801025865A CN 200880102586 A CN200880102586 A CN 200880102586A CN 101970572 A CN101970572 A CN 101970572A
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methyl
mentioned
photocurable composition
amine
group
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CN101970572B (en
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福井弘司
近藤峻右
有光晃二
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Tokyo University of Science
Sekisui Chemical Co Ltd
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Tokyo University of Science
Sekisui Chemical Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/2815—Monohydroxy compounds
    • C08G18/282—Alkanols, cycloalkanols or arylalkanols including terpenealcohols
    • C08G18/2825—Alkanols, cycloalkanols or arylalkanols including terpenealcohols having at least 6 carbon atoms
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
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    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
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    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
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    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/062—Copolymers with monomers not covered by C09J133/06
    • C09J133/068—Copolymers with monomers not covered by C09J133/06 containing glycidyl groups
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • C—CHEMISTRY; METALLURGY
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00—Crosslinking
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  • Polymers & Plastics (AREA)
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  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Epoxy Resins (AREA)
  • Materials For Photolithography (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Polymerisation Methods In General (AREA)
  • Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
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Abstract

The invention provides a photocurable composition which contains a photobase generator capable of generating a satisfactory amount of a base in a high quantum yield when irradiated even with a small quantity of light for a short time and which can be speedily cured by the base into a cured article. A photocurable composition comprising a photobase generator (A) which is a salt of a carboxylic acid (a1-1) represented by the general formula (1-1) with a basic compound (a2) and a curable compound (B) having at least two functional groups selected from among epoxy, (meth)acryloyl, isocyanato, acid anhydride groups, and alkoxysilyl: (1-1) wherein R1 to R7 are each hydrogen or an organic group and may be the same or different, or alternatively two of R1 to R7 may be bonded to each other to form a ring structure.

Description

Photocurable composition
Technical field
The present invention relates to the Photocurable composition containing Photobase generator and curability compound, in more detail, it is related to a kind of Photocurable composition, in the Photocurable composition, alkali is produced by Photobase generator by irradiation light, recycle the alkali to carry out the solidification of curability compound, so as to obtain solidfied material.
Background technology
A kind of known Photocurable composition, it includes compound and curability compound by being solidified as the alkali produced by the compound that alkali is produced by irradiation light.The Photocurable composition is used for bonding agent, adhesive, coating, coating agent, resist and sealant etc..
It is used as the compound that alkali is produced above by irradiation light, it is known to cobalt Complexes, carbamic acid adjacent nitro benzyl ester and oxime ester etc..These compounds produce amine by irradiation light.But, the quantum yield of the amine produced by irradiation light is low.Therefore, the research for the quantum yield for improving amine has been carried out.
As one of the compound for the quantum yield that can improve amine, Patent Document 1 discloses the compound for producing amine represented by following formula (X)s with carbamyl oxyimino group by irradiation light following.
[chemical formula 1]
Figure GPA00001022289300011
It should be noted that in above-mentioned formula (X), R1 is the organic group of n valencys, R2 and R3 are hydrogen, aromatic group or aliphatic group respectively, and n is more than 1 integer.
In addition, in following patent documents 2, disclosing a kind of photosensitive composite, the photosensitive composite contains the salt and macromolecule precursor that the carboxylic acid of decarboxylation is formed with amine by irradiation light.In the patent document, salt that Ketoprofen (ketoprofen, Ketoprofen) and amine formed is described as the compound that amine is produced by irradiation light.In addition, as macromolecule precursor, having used polyimide precursor or polybenzoxazole precursor etc..
In addition, in following non-patent literatures 1, disclosing a kind of photo-curing material, the photo-curing material contains the salt and alkali reaction resin that Ketoprofen and amine described in patent document 2 are formed.As above-mentioned alkali reaction resin, liquid-state epoxy resin has been used.
Patent document 1：Japanese Unexamined Patent Publication 2002-138076 publications
Patent document 2：Japanese Unexamined Patent Publication 2007-101685 publications
Non-patent literature 1：There is the work such as light,《Polymer science can give original text collection》, distribution on May 25th, 2005, page 1357
The content of the invention
For patent document 1 record the compound of amine is produced by irradiation light for, its light decomposability is excellent, with high quantum yield can produce amine by irradiation light.But, although the quantum yield of its amine is higher, but still requires that higher quantum yield.
In addition, it is necessary to which it can rapidly solidify in the presence of the alkali that irradiation light is produced for producing the curability compound that the compound of alkali is applied in combination with irradiation light.
In above-mentioned patent document 2, as above-mentioned curability compound, macromolecule precursor has been used.The macromolecule precursor is macromolecule in itself, can carry out Intra-molecular condensation.By the reaction, the photosensitive composite containing macromolecule precursor solidifies, and shows by resulting solidfied material final target properties.Such macromolecule precursor is not configured as the reaction by macromolecule precursor come the structure of the molecular weight of the reactant obtained by increasing.It is difficult to the reaction by macromolecule precursor to increase molecular weight to show final target properties.
In addition, in order to be adjusted to even if the viscosity that also can be easily coated without using solvent, when using the relatively low macromolecule precursor of molecular weight as above-mentioned macromolecule precursor, further to reduce the molecular weight of above-mentioned reactant.Now, the cohesiveness reduction of the solidfied material after photosensitive, can not fully show cementability and adaptation sometimes.
In addition, for the photo-curing material described in above-mentioned non-patent literature 1, although the hardness of the solidfied material after photosensitive is improved, but sufficient cementability can not be obtained sometimes.
It is a primary object of the present invention to provide a kind of Photocurable composition, wherein, the quantum yield of the alkali produced by Photobase generator is high, the alkali of sufficient amount can be produced in the case of short time and a small amount of irradiation light, alkali produced by recycling promptly carries out the solidification of curability compound, so as to obtain solidfied material.Another object of the present invention is to provide a kind of Photocurable composition, the Photocurable composition particularly can produce the alkali of sufficient amount in the case of short time and a small amount of irradiation light, alkali produced by recycling promptly carries out the solidification of curability compound, so as to show high adhesiveness.
According to the present invention, a kind of Photocurable composition can be provided, it contains Photobase generator (A) and curability compound (B), and the Photobase generator (A) is the salt that the carboxylic acid (a1-1) and alkali compounds (a2) represented by following formula (1-1) is formed；Also, in the curability compound (B), at least there are 2 functional groups selected from epoxy radicals, (methyl) acryloyl group, NCO, anhydride group and alkoxysilyl in a molecule；
[chemical formula 2]
Figure GPA00001022289300031
In above-mentioned formula (1-1), R1~R7 represents hydrogen or organic group respectively, and R1~R7 is identical or different, and 2 in R1~R7 are optionally mutually bonded and form cyclic structure.
In the ad hoc fashion of the present invention, 1 in R3~R7 in above-mentioned formula (1-1) is the organic group that following formula (1-2) is represented.
[chemical formula 3]
Figure GPA00001022289300032
In above-mentioned formula (1-2), R8~R12 represents hydrogen or organic group respectively, and R8~R12 is identical or different, and 2 in R8~R12 are optionally mutually bonded and form cyclic structure.
In another ad hoc fashion of the present invention, the R1 in above-mentioned formula (1-1) is methyl.
In another ad hoc fashion of the present invention, the carboxylic acid (a1-1) that above-mentioned formula (1-1) represents is the carboxylic acid (a1) that following formula (1) is represented.
[chemical formula 4]
In another ad hoc fashion of the present invention, above-mentioned curability compound (B) is the curability compound at least in a molecule with 2 epoxy radicals, and at least one kind of in glycidyl ether type epoxy resin, glycidyl ester epoxy resin and glycidyl amine epoxy resin.
In another ad hoc fashion of the present invention, above-mentioned curability compound (B) is the carbamate prepolymer with NCO.
It is preferred that above-mentioned alkali compounds (a2) is amine.When alkali compounds (a2) is amine, curability compound (B) solidification can be more promptly carried out.
Additionally, it is preferred that having at least two amino in amine described in a molecule.In this case, curability compound (B) solidification can more promptly be carried out.
In the present invention, it is preferred to which above-mentioned amine is the amine represented by any one chemical formula in following formula (2)~(7).In this case, curability compound (B) solidification can more promptly be carried out.
[chemical formula 5]
Figure GPA00001022289300041
[chemical formula 6]
Figure GPA00001022289300042
[chemical formula 7]
(CH3)4N+OH-  (4)
[chemical formula 8]
Figure GPA00001022289300043
In above-mentioned formula (5), R1Represent the alkylidene that carbon number is 1~10.
[chemical formula 9]
H2N-R2-NH2   (6)
In above-mentioned formula (6), R2The alkylidene that carbon number is 1~10 is represented,
[chemical formula 10]
The Photocurable composition of the present invention preferably further contains alkali multiplication agent (C).During containing alkali multiplication agent (C), curability compound (B) solidification can be more promptly carried out.
In addition, the Photocurable composition of the present invention preferably further contains sensitising agent (D).During containing sensitising agent (D), curability compound (B) solidification can be more promptly carried out.
In another ad hoc fashion of the present invention, the mol ratio of the basic functionality of the functional group being selected from epoxy radicals, (methyl) acryloyl group, NCO, anhydride group and alkoxysilyl and the alkali compounds (a2) is in the range of 1: 0.01~1: 2.
In another ad hoc fashion of the present invention, the number-average molecular weight of above-mentioned curability compound (B) divided by the value (number of number-average molecular weight/functional group) obtained from epoxy radicals, (methyl) acryloyl group, NCO, anhydride group and the number of the functional group in alkoxysilyl are in the range of 170~50000.
The Photocurable composition of the present invention can be used in various uses, wherein, preferably Photocurable composition of the invention is used as bonding agent.It is preferred that the Photocurable composition of the present invention is Photocurable adhesive agent composition.In addition, the Photocurable composition of the present invention is further preferably used as coating agent.It is preferred that the Photocurable composition of the present invention is Photocurable coating agent composition.
The effect of invention
For the Photocurable composition of the present invention, because Photobase generator (A) is the salt of the carboxylic acid (a1-1) that above-mentioned formula (1-1) is represented and alkali compounds (a2) formation, therefore, the quantum yield of the alkali produced by Photobase generator (A) is high, and the alkali of sufficient amount can be produced in the case of short time and a small amount of irradiation light.
In addition; the above-mentioned curability compound (B) being applied in combination with Photobase generator (A) in a molecule due at least having 2 functional groups being selected from epoxy radicals, (methyl) acryloyl group, NCO, anhydride group and alkoxysilyl; therefore; can rapidly it solidify in the presence of the alkali produced by the curability compound (B), so as to obtain solidfied material.
The above-mentioned curability compound (B) that is applied in combination with Photobase generator (A) is the curability compound at least in a molecule with 2 epoxy radicals, and during at least one kind of in glycidyl ether type epoxy resin, glycidyl ester epoxy resin and glycidyl amine epoxy resin, can more quickly solidify in the presence of the alkali produced by the curability compound (B).
Embodiment
Below, the details of the present invention is illustrated.
The present inventor etc. are in order to solve the above-mentioned technical problem, to being had made intensive studies containing the Photobase generator that alkali is produced by irradiation light and the Photocurable composition of curability compound, as a result find, by using the combination containing generated base alkaline agent (A) (carboxylic acid (a1-1) and the salt of alkali compounds (a2) formation that i.e. above-mentioned formula (1-1) represents) and above-mentioned specific curability compound (B), the alkali of sufficient amount can be produced in the case of short time and a small amount of irradiation light, alkali produced by recycling makes curability compound (B) solidification rapidly, so as to complete the present invention.
(Photobase generator (A))
The Photobase generator (A) contained in the Photocurable composition of the present invention is the salt of the carboxylic acid (a1-1) that following formula (1-1) is represented and alkali compounds (a2) formation.
[chemical formula 11]
In above-mentioned formula (1-1), R1~R7 represents hydrogen or organic group respectively, and R1~R7 is identical or different, and 2 in R1~R7 are optionally mutually bonded and form cyclic structure.
Additionally, it is preferred that 1 in R3~R7 in above-mentioned formula (1-1) organic group represented for following formula (1-2).
[chemical formula 12]
Figure GPA00001022289300062
In above-mentioned formula (1-2), R8~R12 represents hydrogen or organic group respectively, and R8~R12 is identical or different, and 2 in R8~R12 are optionally mutually bonded and form cyclic structure.
Additionally, it is preferred that the R1 in above-mentioned formula (1-1) is methyl.
The specific example of the carboxylic acid (a1-1) represented as above-mentioned formula (1-1), can be enumerated for example：Phenylacetic acid, diphenyl acetic acid, triphenylacetic acid, 2- phenylpropionic acids, 2,2- diphenyl-propionic acids, 2,2,2- triphenylpropionic acids, 2- phenylbutyric acids, α-methoxyphenyl acetic acid, phenylglycolic acid, phenyl-lactic acid, benzilic acid (benzylic acid), tropic acid (tropic acid), phenylmalonic acid, phenylsuccinic acid, 3- methyl -2- phenylbutyric acids, o-tolyl acetic acid, between tolylacetic acid, 4- isobutyl groups-Alpha-Methyl phenylacetic acid, p-methylphenyl acetic acid, 1,2- phenylenediacetic acid, 1,3- phenylenediacetic acid, Isosorbide-5-Nitrae-phenylenediacetic acid, 2- methoxyphenyl acetic acids, 2- hydroxyphenyl acetic acids, 2- nitro phenyl acetic acids, 3- nitro phenyl acetic acids, 4- nitro phenyl acetic acids, 2- (4- nitrobenzophenones) propionic acid, 3- (4- nitrobenzophenones) propionic acid, 4- (4- nitrobenzophenones) propionic acid, 3,4- dimethoxy benzene guanidine-acetic acids, 3,4- (methylene dioxy) phenylacetic acids, 2,5- dimethoxy benzene guanidine-acetic acids, 3,5- dimethoxy benzene guanidine-acetic acids, 3,4,5- trimethoxy-benzene guanidine-acetic acids, 2,4- dinitro benzene guanidine-acetic acids, biphenylacetic acid, 1- naphthyl acetic acids, 2- naphthyl acetic acids, 6- methoxy-alpha-methyl -2- naphthyl acetic acids, 1- pyrene acetic acid, 9- fluorenes carboxylic acid or 9H- xanthene-9-carboxylic acids etc..
Being mixed in a reservoir only by the carboxylic acid (a1-1) and alkali compounds (a2) that represent above-mentioned formula (1-1) just can easily prepare above-mentioned Photobase generator (A), and without complicated synthesis path.When the carboxylic acid (a1-1) and alkali compounds (a2) that above-mentioned formula (1-1) represents are mixed in a reservoir, the acid-base reaction that following formula (8-1) is represented is carried out, so as to generate salt.
[chemical formula 13]
Figure GPA00001022289300071
Formula (8-1)
In above-mentioned formula (8-1), X represents alkali compounds (a2).
Due to the skeleton with the carboxylic acid (a1-1) represented from above-mentioned formula (1-1), therefore in irradiation light decarboxylation easily occurs for above-mentioned Photobase generator (A), carries out the reaction that following formula (9-1) is represented.Therefore, in the presence of no sensitising agent, simply individually above-mentioned Photobase generator (A) also has excellent light decomposability.That is, the quantum yield of the alkali produced by above-mentioned Photobase generator (A) is high, and the alkali of sufficient amount can be produced in the case of short time and a small amount of irradiation light.
[chemical formula 14]
Figure GPA00001022289300072
Formula (9-1)
In above-mentioned formula (9-1), X represents alkali compounds (a2).
It should be noted that R1~R7 in above-mentioned formula (8-1) and (9-1) represents hydrogen or organic group respectively.R1~R7 can be the same or different.2 in R1~R7 are optionally mutually bonded and form cyclic structure.
The carboxylic acid (a1-1) that particularly preferred above-mentioned (1-1) is represented is the carboxylic acid (a1) that following formula (1) is represented.The light decomposition efficiency for the carboxylic acid (a1) that following formula (1) is represented is especially excellent.
[chemical formula 15]
Figure GPA00001022289300081
When the carboxylic acid (a1) and alkali compounds (a2) that above-mentioned formula (1) represents are mixed in a reservoir, the acid-base reaction that following formula (8) is represented is carried out, so as to generate salt.
[chemical formula 16]
Figure GPA00001022289300082
Formula (8)
In above-mentioned formula (8), X represents alkali compounds (a2).
In addition, decarboxylation easily occurs in irradiation light for salt obtained from the acid-base reaction represented by above-mentioned formula (8), the reaction that following formula (9) is represented is carried out.
[chemical formula 17]
Figure GPA00001022289300083
Formula (9)
In addition, the carboxylic acid (a1-1) represented as above-mentioned formula (1-1), preferably uses carboxylic acid (a1-3)~(a1-6) of following formula (1-3)~(1-6) expressions.
[chemical formula 18]
Figure GPA00001022289300084
[chemical formula 19]
Figure GPA00001022289300085
[chemical formula 20]
Figure GPA00001022289300091
[chemical formula 21]
Figure GPA00001022289300092
Above-mentioned alkali compounds (a2) is not particularly limited.As above-mentioned alkali compounds (a2), amine, the compound containing pyridine radicals, hydrazine compound, amide compound, quaternary ammonium hydroxide, sulfhydryl compound, sulfide compound or phosphine compound can be enumerated.
Above-mentioned amine is not particularly limited.As above-mentioned amine, arbitrary amine in primary amine, secondary amine and tertiary amine can be used.
As above-mentioned primary amine, it can enumerate for example：Methylamine, ethamine, n-propylamine, n-butylamine, amylamine, n-hexylamine, positive heptyl amice, n-octyl amine, positive nonyl amine, n-Decylamine, n-undecane amine, n-dodecane amine, n-tridecane amine, n-tetradecane amine, n-pentadecane amine, hexadecane amine, n-octadecane amine, isopropylamine, isobutyl amine, sec-butylamine, tert-butylamine, 1- methylbutylamines, 1- ethylpropylamines, iso-amylamine, 1,2- dimethyl propylamine, tertiary amylamine, 1,3- dimethyl butylamine, 3,3- dimethyl butylamines, 2-aminoheptane, 3- aminoheptanes, 1- methylaminoheptanes, 2 ethyl hexylamine, 1,5- dimethylhexylamine, t-octanylamine, ethylenediamine, 1,3- diaminopropanes, 1,2- diaminopropanes, 1,4-Diaminobutane, 1,2- diaminourea -2- methylpropanes, 1,5- 1,5-DAP, 1,3- 1,5-DAP, 1,5- diaminourea -2- methylpentanes, 1,7- diaminoheptane, 1,8- diamino-octane, 1,9- diamino nonane, 1,10- diamino decane, 1,12- diamino dodecane, 2- butyl -2- ethyl -1,5- pentanediamines, cyclopropylamine, (amino methyl) cyclopropane, ring butylamine, cyclopentamine, 5- amino -2,2,4- trimethyl -1- cyclopentanemethylamines, cyclohexylamine, 2- tuaminoheptanes, 4- methyl cyclohexylamines, 4,4 '-di-2-ethylhexylphosphine oxide (cyclohexylamine), 2,3- dimethyl cyclohexyl amines, 4,4 '-di-2-ethylhexylphosphine oxide (2- methyl cyclohexylamines), 1,2- diaminocyclohexane, cyclohexane methylamine, 1,8- diaminourea pair
Figure GPA00001022289300093
Alkane,5- amino -1,3,3- trimethyl-cyclohexane methylamines,Cycloheptylamine,Cyclooctylamine,Cyclododecane amine,2- amino ENBs,Borneol amine,6,Bicyclic [3.1.1] heptane -2 β of 6- dimethyl-methane amine (myrtanylamine),1- amantadines,1- adamantane methylamines,Allylamine,Oleyl amine,Spiceleaf amine (ゼ ラ ニ Le ア ミ Application,Geranylamine),2,2,2- trifluoro methylamines,2- methoxyethyl amines,3 methoxypropyl amine,3- ethoxy propylamines,3- butoxy propyl amines,2- amino -1- methoxy propanes,3- isopropoxy propylamine,2,2 '-oxygen connection is double (ethylene amines),2,2 '-(ethylidene dioxy) is double (ethamine),4,9- dioxas -1,12- dodecamethylene diamines,4,7,10- trioxas -1,13- tridecane diamines,3- amino -1- propyl alcohol vinyl ethers,Tetrahydrofurfuryl amine,2,5- dihydros -2,5- dimethoxy chaff amine,Aminoacetaldehyde dimethyl acetal,4- aminobutyl aldehyde diethyl acetals,Monoethanolamine,3- amino -1- propyl alcohol,2- amino -1- propyl alcohol,1- amino -2- propyl alcohol,4- amino-n-butyl alcohol,2- amino-n-butyl alcohol,2-amino-2-methyl-1-propanol,5- amino -1- amylalcohols,2- amino -1- amylalcohols,2- amino -3- methyl-1-butanols,6- amino -1- hexanols,2- amino -1- hexanols,1- amino -1- cyclopentanemethanols,2- aminocyclohexanols,4- aminocyclohexanols,1- aminomethyl-1,2s-cyclohexanol,3- amino methyls -3,5,5- trimethyl-cyclohexanes,2- (2- amino ethoxies) ethanol,2- (methylamino) ethanol,2- (ethylamino) ethanol,2- (propylcarbamic) ethanol,2- (tert-butylamino) ethanol,3- amino -1,2- propane diols,SERINOL,2- amino -2- ethyls -1,Ammediol,2- amino-2-methyls -1,Ammediol,Three (hydroxymethyl) aminomethanes,BIS-HOMOTORIS,1,3- diaminourea -2- hydroxy propanes,1- amino-deoxysorbitol,2- aminomethyl-1,2 5- crown-s 5,2- aminomethyl-1,2 8- crown-s 6,Aniline,Ortho-aminotoluene,Meta-aminotoluene,Para-totuidine,2- MEAs,3- MEAs,4- MEAs,2- propyl group aniline,3- propyl group aniline,4- propyl group aniline,2- isopropyl anilines,3- isopropyl anilines,4- isopropyl anilines,2- butylanilines,3- butylanilines,4- butylanilines,2- sec-butyl aniline,3- sec-butyl aniline,4- sec-butyl aniline,2- tert-butyl group aniline,3- tert-butyl group aniline,4- tert-butyl group aniline,4- amyl anilines,4- hexyl aniline,4- heptyl aniline,4- octyl group aniline,4- decyl aniline,4- dodecyl polyanilines,4- myristyl aniline,4- hexadecylanilines,4- cyclohexyl aniline,2,2 '-ethylene aniline,O-aminoanisole,M-anisidine,P-nethoxyaniline,O-ethoxyl amine,M-oxethyl aniline,P-ethoxyaniline,Ortho-Aminophenol,3- amino-phenols,PAP,2- aminothiophenols,3- aminothiophenols,4- aminothiophenols,2- aminobenzyl alcohols,2- aminophenyl ethanol,3- aminophenyl ethanol,4- aminophenyl ethanol,3- (1- hydroxyethyls) aniline,2- (methyl mercapto) aniline,3- (methyl mercapto) aniline,4- (methyl mercapto) aniline,2- aminophenyl disulfides,2- isopropenyl aniline,4,4 '-ethylene aniline,3,3 '-methylene dianiline (MDA),4,4 '-methylene dianiline (MDA),4,4 '-di-2-ethylhexylphosphine oxide (3- chloro- 2,6- diethylanilines),4,4 '-diaminourea Stilbene,4- butoxy anilines,4- amoxy aniline,4- hexyloxy aniline,4,4 '-oxydiphenyl amine,4,4 '-sulphur di- aniline,4”,4 " "-(hexafluoroisopropyli,ene)-bis--(4- phenylanilines),Oxydiphenyl amine,4- aminophenyl-thioethers,2,3- dimethylanilines,2,4- dimethylanilines,2,5- dimethylanilines,2,6- dimethylanilines,3,4- dimethylanilines,3,5- dimethylanilines,6- ethyl-ortho-toluidines,2,6- diethylanilines,2- isopropyl -6- methylanilines,2,6- diisopropyl anilines,1- amino -5,6,7,8- naphthanes,5- amino indenes,2- fluoroanilines,3- fluoroanilines,4- fluoroanilines,2- chloroanilines,3- chloroanilines,4- chloroanilines,2- bromanilines,3- bromanilines,4- bromanilines,2- Iodoanilines,3- Iodoanilines,4- Iodoanilines,2- (trifluoromethyl) aniline,3- (trifluoromethyl) aniline,4- (trifluoromethyl) aniline,3- (trifluoromethoxy) aniline,4- (trifluoromethoxy) aniline,3-(1,1,2,The fluoro ethyls of 2- tetra-) aniline,3- fluoro-2-methylbenzene amine,3- chloro-2-methyl anilines,The chloro- 6- methylanilines of 2-,2,6- difluoroanilines,2,3- difluoroanilines,2,6- dichloroanilines,2,3- dichloroanilines,2,6- dibromo anilines,2- methoxyl group -6- methylanilines,3- fluorine o-aminoanisoles,3- amino-2-methyl benzylalcohols,2- amino -3- xylyl alcohols,2- amino m-cresols,2,3- diaminophenols,Ortho-aminotoluene,4,4 '-ethylene meta-aminotoluene,2,5- di-tert-butyl anilines,The fluoro- 4- methylanilines of 3-,The fluoro- 4- methylanilines of 2-,5- fluoro-2-methylbenzene amine,The fluoro- 5- methylanilines of 2-,4- fluoro-2-methylbenzene amine,The fluoro- 6- methylanilines of 2-,2,Double (trifluoromethyl) aniline of 5-,2- fluoro- 6- (trifluoromethyl) aniline,2- fluoro- 3- (trifluoromethyl) aniline,2,4- difluoroanilines,3,4- difluoroanilines,2,5- difluoroanilines,The chloro- 4- fluoroanilines of 3-,The chloro- 4- fluoroanilines of 2-,The bromo- 4- fluoroanilines of 2-,The bromo- 2- fluoroanilines of 4-,The bromo- 4- Iodoanilines of 2-,The chloro- 4- amino toluenes of 2-,The chloro- 4- methylanilines of 2-,The chloro- 5- methylanilines of 2-,5- chloro-2-methyl anilines,4- chloro-2-methyl anilines,3,4- dichloroanilines,2,4- dichloroanilines,2,5- dichloroanilines,The bromo- 2-aminotoluenes of 4-,The bromo- 3- methylanilines of 4-,The bromo- 4- methylanilines of 3-,The bromo- 4- methylanilines of 2-,The bromo- 2- chloroanilines of 4-,2,4- dibromo anilines,2,5- dibromo anilines,4- fluoro- 2- (trifluoromethyl) aniline,4- fluoro- 3- (trifluoromethyl) aniline,2- fluoro- 5- (trifluoromethyl) aniline,4- chloro- 3- (trifluoromethyl) aniline,4- chloro- 2- (trifluoromethyl) aniline,4- bromo- 2- (trifluoromethyl) aniline,4- bromo- 3- (trifluoromethyl) aniline,2- bromo- 5- (trifluoromethyl) aniline,2- chloro- 5- (trifluoromethyl) aniline,5,5 '-(hexafluoroisopropyli,ene) two ortho-aminotoluenes,4- methoxyl groups -2-aminotoluene,2- methoxyl group -5- methylanilines,5- methoxyl groups -2-aminotoluene,5- tert-butyl o aminoanisoles,2- methoxyl groups -5- (trifluoromethyl) aniline,6- chlorine m-anisidines,4- amino 1,2-dimethoxy benzene (veratrole),3,4- (methylene dioxy) aniline,Benzo 1,4- dioxane -6- amine,4 '-amino Benzo15crown5 derivatives 5,2,4- dimethoxyanilines,4- amino orthoresols,2,5- dimethoxyanilines,5- amino -2- metoxyphenols,3- amino orthoresols,2- amino orthoresols,2- amino-tert-butyl phenol,2- amino-tert-amyl phenol,6- amino m-cresols,4- amino m-cresols,2- amino -5- xylyl alcohols,3- amino -4- xylyl alcohols,2- amino -4- chlorophenols,4- amino -3- chlorophenols,2- amino -5- chlorobenzyl alcohols,5- chlorine o-aminoanisoles,3- fluorine P-nethoxyaniline,3- chlorine P-nethoxyaniline,2- amino -4- (trifluoromethyl) benzenethiol,3,5- dimethylanilines,3,5- di-tert-butyl anilines,3,Double (trifluoromethyl) aniline of 5-,3,5- difluoroanilines,3,5- dichloroanilines,3,5- dimethoxyanilines,3- methoxyl groups -5- (trifluoromethyl) aniline,2,4,6- trimethylanilines,4,4 '-di-2-ethylhexylphosphine oxide (2,6- dimethylanilines),4,4 '-di-2-ethylhexylphosphine oxide (2,6- diethylanilines),4,4 '-di-2-ethylhexylphosphine oxide (2,6- diisopropyl anilines),2,4,6- tri-tert aniline,2- chloro- 4,6- dimethylanilines,2,The chloro- 3- methylanilines of 6- bis-,3- chloro- 2,4- difluoroanilines,2,3,4- trichloroanilines,2,3,4- trifluoromethyl anilines,2,3,6- trifluoromethyl anilines,2,4,6- trifluoromethyl anilines,2,The bromo- 4- methylanilines of 6- bis-,3- chloro- 2,6- diethylanilines,4- bromo- 2,6- dimethylanilines,2- chloro- 3,5- difluoroanilines,4- bromo- 2,6- difluoroanilines,The chloro- 6- fluoroanilines of the bromo- 4- of 2-,2,The bromo- 6- fluoroanilines of 4- bis-,2,The bromo- 4- fluoroanilines of 6- bis-,2,6- bis- chloro- 4- (trifluoromethyl) aniline,4- chloro- 2,6- dibromo anilines,4- amino -2,6- chlorophenesic acids,3,4,5- trichloroanilines,3,4,5- trimethoxy-anilines,3,3’,5,5 '-tetramethyl benzidine,2- bromo- 4,6- difluoroanilines,2,4,6- trichloroanilines,2,6- bis- chloro- 4- (trifluoromethoxy) aniline,2- bromo- 3,Double (trifluoromethyl) aniline of 5-,2,4,6- tribromanilines,The fluoro- 5- methylanilines of the chloro- 4- of 2-,2,4,5- trifluoromethyl anilines,2,4,5- trichloroanilines,The chloro- 2- methoxyl groups -5- methylanilines of 4-,4- amino -2,5- xylenols,4- amino -2,6- dibromophenols,3,5- bis- chloro- 2,6- diethylanilines,2,3,5,6- tetrachloro anilines,2,3,5,6- tetrafluoroanilines,2,3,4,5- tetrafluoroanilines,2,3,4,6- tetrafluoroanilines,2- bromo- 3,4,6- trifluoromethyl anilines,2- bromo- 4,5,6- trifluoromethyl anilines,2- amino -2,The chloro- 3- methylphenols of 4- bis-,2,3,5,The fluoro- 4- 5-trifluoromethylanilines of 6- tetra-,2,3,4,5,6- pentafluoroanilines,4,4 '-diaminourea octafluorobiphenyl,4- methoxyl group -3- benzidine,4- bromo- 2,3,5,6- tetrafluoroanilines,1,2- phenylenediamines,2,3- diaminotoluenes,3,4- diaminotoluenes,3,3 '-diaminobenzidine,4- chloro- 1,2- phenylenediamines,4- methoxyl groups -1,2- phenylenediamines,4,5- dimethyl -1,2- phenylenediamines,1,2,4,5- benzene tetramines,4,5- bis- chloro- 1,2- phenylenediamines,1,3- phenylenediamines,2,6- diaminotoluenes,2,4- diaminotoluenes,2,4,6- trimethyls -1,3- phenylenediamines,4- methoxyl groups -1,3- phenylenediamines,2,4- diaminophenols,4- (2- hydroxyeththylthios) -1,3- phenylenediamines,1,4- phenylenediamines,2,5- diaminotoluenes,2,5- dimethyl -1,4- phenylenediamines,2- chloro- 1,4- phenylenediamines,2,5- bis- chloro- 1,4- phenylenediamines,2- methoxyl groups -1,4- phenylenediamines,2,3,5,6- tetramethyls -1,4- phenylenediamines,2- aminobphenyls,4- aminobphenyls,2,4,6- triphenyl aniline,2- amino-4-phenyl phenol,5- phenyl o-aminoanisoles,Benzylamine,Alpha-Methyl benzylamine,Aminodiphenylmethane,Triphenyl amine,1,2- diphenyl-ethyl amine,2,2- diphenylethlene amine,2- amino -1,2- diphenyl ethanol,Phenyl ethylamine,2- amino -3- phenyl-1-propanols,2- phenyl cyclopropylamines,3- phenyl -1- propylamine,3,3- diphenylpropylamines,1- methyl -3- phenylpropylamines,4- phenyibutylamines,1,2- diphenyl ethylene diamines,1,Double (4- methoxyphenyls) ethylenediamines of 2-,4-(2,The tert-amyl benzene epoxides of 4- bis-) butylamine,2- amino -1- phenylethanols,2- phenylqlvcinols (glycinol),2- amino -3- phenyl-1-propanols,NOREPHEDRINE,2- methylbenzylamines,1- amino indenes,2- amino indenes,1,2,3,4- tetrahydrochysene -1- naphthylamines,2- (trifluoromethyl) benzylamine,2- fluorin benzyl amines,2- fluorophenethylamines,2- chlorobenzylamines,2- chlorophenethylamines,2- bretylium tosylates,2- methoxybenzylamines,2- methoxyphenethylamines,2- ethyoxyl benzylamines,2- [2- (amino methyl) thiophenyl] benzylalcohol,2- amino-benzylamines,3- methylbenzylamines,3- (trifluoromethyl) benzylamine,M-xylene diamine,3- fluorin benzyl amines,3- fluorophenethylamines,3- chlorobenzylamines,3- chlorophenethylamines,3- bretylium tosylates,3- iodine benzylamines,3- methoxyphenethylamines,4- methylbenzylamines,P dimethylamine,4- (trifluoromethyl) benzylamine,α,4- dimethyl benzylamines,2- (toluoyl) ethamine,4- fluorin benzyl amines,4- fluorophenethylamines,4- chlorobenzylamines,4- bretylium tosylates,4- Bretylium Tosylates,4- fluoro-alphas-methylbenzylamine,4- fluorophenethylamines,4- chlorophenethylamines,4- methoxybenzylamines,4- methoxyphenethylamines,4- (trifluoromethoxy) benzylamine,4- amino-benzylamines,2- (4- aminophenyls) ethylamine,TYRAMINE,3,Double (trifluoromethyl) benzylamines of 5-,3- fluoro- 5- (trifluoromethyl) benzylamine,2,6- difluorobenzylamines,2,4- difluorobenzylamines,2,5- difluorobenzylamines,3,4- difluorobenzylamines,2,4- dichloro-benzylamines,3,4- dichloro-benzylamines,2,4- dichloro-phenylethylamines,2,3- dimethoxybenzylamines,3,5- dimethoxybenzylamines,2,4- dimethoxybenzylamines,3,4- dimethoxybenzylamines,2,5- dimethoxy-phenylethylamines,3,4- dimethoxy-phenylethylamines,Pepper amine,3,4,5- trimethoxy benzylamines,2,4,6- trimethoxy benzylamines,1- Aminoindazoles,1- naphthalene methylamines,1- (1- naphthyls) ethamine,9- aminofluorenes,1- pyrene methylamines,α,ω-diaminourea polyethylene glycol,α,ω-diaminourea polypropylene glycol,α,ω-diaminourea dimethyl silicone polymer or polyallylamine etc..
As above-mentioned secondary amine, it can enumerate for example：Dimethylamine,N- ethyl dimethylamines,Diethylamine,N methyl pmpyl amine,N-methylisopropylamine,N- ethyl isopropylamines,Di-n-propylamine,Diisopropylamine,N- methylbutylamines,N- ethyl butyl amines,N- methyl tert-butylamines,N- tert-butyl group isopropylamines,Dibutyl amine,Di-sec-butylamine,Di-iso-butylmanice,Tertiary pentyl tert-butylamine,Diamylamine,N- tuaminoheptanes,Dihexylamine,Tertiary pentyl t-octanylamine,Dioctylamine,Double (2- ethylhexyls) amine,Didecylamine,N- methyl octadecylamines,N,N '-dimethyl ethylenediamine,N,N '-diethyl ethylenediamine,N,N '-diisopropyl ethylenediamine,N,N '-dimethyl -1,3- propane diamine,N,N '-diethyl -1,3- propane diamine,N,N '-diisopropyl -1,3- propane diamine,N,N '-dimethyl -1,6- hexamethylene diamines,N- propyl group cyclopropanemethylamines,N-methylcyclohexylamine,N- ethyl cyclohexylamines,N- isopropyl cyclohexylamine,N- t-butylcyclohexyl amine,Dicyclohexyl amine,N,N '-bis- (3,3- dimethylbutyls) -1,2- cyclohexane diamines,1- cyclohexylethylamines,1,3- hexamethylenes (dimethylamine),N- methyl allyl amines,N- methyl -2- methyl allyl amines,Diallylamine,N,N '-diethyl -2- butene-1s,4- diamines,N- pi-allyl cyclopentamines,N- pi-allyl cyclammonium,2- (1- cyclohexene) ethamine,6- (dimethylamino) fulvene,Double (2- methoxy ethyls) amine,Methylamino dimethylacetal,Diethylamino diethylacetal,2- methylaminoethyls -1,3- dioxolanes,Diethanol amine,Diisopropanolamine (DIPA),N,N '-bis- (2- hydroxyethyls) ethylenediamine,1,Double [three (hydroxymethyl) methylaminos] propane of 3-,N-METHYL-ALPHA-L-GLUCOSAMINE,2- methyl-aziridinyl propane,Azetidine,Pyrrolidines,2,5- dimethyl pyrrolidines,3- pyrrolidinols,2- pyrrolidine carbinols,3- pyrrolins,2,5- dimethyl -3- pyrrolins,Piperidines,1,2,3,6- tetrahydropyridines,Pipecoline,2- ethyl piperidines,3- methyl piperidines,4- methyl piperidines,4,4 '-connection piperidines,4,4 '-ethylidene joins piperidines,4,4 '-trimethylene joins piperidines,3,3- lupetidines,2,6- lupetidines,3,5- lupetidines,2,2,6,6- tetramethyl piperidines,1,4- dioxa -8- azaspiros [4.5] decane,2- piperidine carbinols,2- piperidine ethanols,3- hydroxy piperidines,3- piperidine carbinols,4- hydroxy piperidines,2,2,6,6- trimethyl -4- piperidine alcohols,7,7,9,9- tetramethyls -1,4- dioxa -8- azaspiros [4.5] decane -2- methanol,Hexamethylene imine,Heptamethylene imines,Piperazine,2- methyl piperazines,2,6- lupetazins,2,5- lupetazins,Homopiperazine,Acetaldehyde ammonia tripolymer,1,4,7- 7-triazacyclononanes,1,5,9- triazododecanes,CYCLEN,1,4,8,11- tetraazacyclododecane tetradecanes,1,4,8,12- tetraazacyclododecane pentadecanes,HEXACYCLEN,1,3,3- trimethyl -6- azabicyclos [3.2.1] octane,Ten EEDQs,Sparteine (sparteine),4,4- bis- Jia Ji oxazolidines (オ キ サ De リ ジ Application),4- Ethyl-2-Methyls -2- (3- methyl butyl) oxazolidines,Morpholine,2,6- thebaines,1- azepines -12-crown-4,1- azepine -15- crown-s 5,1- azepine -18- crown-s 6,1,4,10- trioxas -7,13- diazacyclo pentadecanes,1,4,10,The oxa-s -7 of 13- tetra-,16- diazacyclo octadecanes,Thiazolidine,Thiomorpholine,Methylphenylamine,N-ethylaniline,N- butylanilines,Diphenylamine,N- phenylbenzylamines,1,2- hexichol ethylamines,N- pi-allyl aniline,2- ethoxylanilines,N- ethyl-ortho-toluidines,N-ethyl-m-toluidine,N- ethyl-p-toluidiines,4- chloro-n-methyl aniline,N- methyl P-nethoxyaniline,4- amino methyl phenol,N- ethyls -2,3- dimethylanilines,N- ethyls -3,4- (methylene dioxy) aniline,2,4,6- tri-terts-methylphenylamine,N,N '-diphenyl -1,4- phenylenediamines,N,N '-diphenylbenzidine,3,3 '-(hexafluoroisopropyli,ene) diphenylamines,4,4 '-(hexafluoroisopropyli,ene) diphenylamines,2- benzylanilines,1- amino -4- bromonaphthalenes,1- amino-beta naphthal,4- amino -1- naphthols,5- amino -1- naphthols,3- amino-beta naphthal,2,2 '-two sulphur are double (1- naphthalenes),2,3- diaminonaphthalenes,1,5- diaminonaphthalenes,1,8- diaminonaphthalenes,1,1 '-binaphthyl -2,2 '-diamines,1- aminofluorenes,2- aminofluorenes,2,7- diamino-fluorenes,3,7- diaminourea -2- methoxyl group fluorenes,2- amino -7- bromine fluorenes,2- amino -9- hydroxyphenyl fluorenes,The bromo- 9- hydroxyphenyl fluorenes of 2- amino -3-,1- amino anthracenes,2- amino anthracenes,9- aminophenanthrenes,9,10- diaminourea is luxuriant and rich with fragrance,The glimmering province of 3- amino,1- amino pyrenes,6- amino bends (Network ラ イ セ Application,6-aminochrysene),N,Alpha-alpha-dimethyl benzylamine,N- benzyl-alphas-methylbenzylamine,N- benzylmethylamines,N- Ethylbenzyl methylamines,N- isopropyl benzyl methylamines,N- butyl benzyl methylamines,N- t-butylbenzyl methylamines,Dibenzylamine,N,N '-dibenzyl-ethylenediamin,N- Methylphenethylamines,N- benzyl -2- phenyl ethylamines,Beta-methyl phenyl ethylamine,N- benzyl ethyl alcohol amine,2- (benzylamino) cyclohexane methanol,α-(Methylaminomethyl) benzylalcohol,EPHEDRINE,α-diphenyl -2- pyrrolidine carbinols,4- benzyl diethylenediamines,4- phenyl -1,2,3,6- tetrahydropyridines,Dihydroindole,2 methyl indole is expired,1,2,3,4- tetrahydro carbazoles,2,3- dimethyl indoles are expired,Dihydroindole -2- carboxylic acids,1,2,3,4- tetrahydroquinolines,1,2,3,4- tetrahydroisoquinolines,6,7- dimethoxys -1,2,3,4- tetrahydroisoquinolines,Iminodibenzyl,5,6,11,12- tetrahydrochysene dibenzo [B,F] azocine (azocine),Benzodiazine (Off エ ノ ザ ジ Application) or phenthazine etc..
As above-mentioned tertiary amine, it can enumerate for example：Trimethylamine,N,N- dimethyl amines,N,N- diethyl methyl amines,Triethylamine,Tripropyl amine (TPA),N,N- dimethylisopropylamines,N,N- diisopropylethylamine,N,N- dimethyl butylamines,N- methyl dibutyl amine,Tri-n-butylamine,Triisobutylamine,Triamylamine,N,N- dimethylhexylamines,Trihexylamine,N,N- dimethyl octylames,N- MDOA methyldioctylamines,Trioctylamine,Tri-iso-octylamine,Three isodecyl amines,N,N- dimethyl heptadecyl-amines,N,N- dimethyl dodecyl amines,Tridodecylamine,N- methyl two (octadecyl) amine,N,N,N’,N '-tetramethyl diaminomethane,N,N,N’,N '-tetramethylethylenediamine,N,N,N’,N '-tetraethylethylenediamine,N,N,N’,N '-tetramethyl -1,3- propane diamine,N,N,N’,N '-tetraethyl -1,3- propane diamine,N,N,N’,N '-tetraethyl -1,3- butane diamines,N,N,N’,N '-tetramethyl -1,4- butane diamines,N,N,N’,N '-tetramethyl -1,5- pentanediamines,N,N,N’,N '-tetramethyl -1,6- hexamethylene diamines,N,N,N’,The N '-tetrabutyl -1,6- hexamethylene diamines,Three (dimethylamino) methane,N,N,N’,N’,N "-five methyl diethylentriamine,N,N- dimethyl cyclohexyl amines,N,N- diethyl cyclohexylamines,N- methyldicyclohexylamines,N- ethyl dicyclohexyl amines,N,N- dimethyl cyclohexane methylamines,Triallylamine,Three (2- methacrylics) amine,N,N,N’,N '-tetramethyl -2- butene-1s,4- diamines,Four (dimethyl) amino ethene,Perfluor isobutyl amine,Three [2- (2- methoxy ethoxies) ethyl] amine,Double (dimethylamino) methane of tert-butoxy,2- (diethylamino) ethanol vinyl ethers,N,N '-dimethyl formamide dimethyl acetal,N,N '-dimethyl formamide diethyl acetal,N,N '-dimethyl formamide two propyl alcohol of contracting,N,N '-dimethyl formamide contracting diisopropanol,N,N '-dimethyl formamide two tert-butyl alcohols of contracting,N,N '-dimethyl formamide two neopentyl alcohols of contracting,N,N '-dimethyl formamide contracting dicyclohexano,N,N- dimethyl acetamide dimethyl acetals,Dimethylamino diethylacetal,Diethylamino diethylacetal,N,N '-bis- (2,2- dimethoxy-ethyls) methylamine,N,N- dimethylethanolamines,N,N- diethyl ethylene diamines,2- (diisopropylaminoethyl) ethanol,2- (dibutylamino) ethanol,3- dimethylamino -1- propyl alcohol,3- diethylamino -1- propyl alcohol,1- dimethylamino -2- propyl alcohol,1- diethylamino -2- propyl alcohol,2- dimethylaminos -2- methyl isophthalic acids-propyl alcohol,5- diethylamino -2- amylalcohols,N methyldiethanol amine,N- ethyldiethanolamines,N butyl diethanol amine,1-[N,Double (2- hydroxyethyls) amino of N-] -2- propyl alcohol,Triisopropanolamine,3- (dimethylamino) -1,2- propane diols,3- (diethylamino) -1,2- propane diols,3- (dipropylamino) -1,2- propane diols,3- (diisopropylaminoethyl) -1,2- propane diols,2- { [2- (dimethylamino) ethyl] methylamino } ethanol,1,Double (the dimethylamino) -2- propyl alcohol of 3-,N,N,N’,N '-four (2- hydroxypropyls) ethylenediamine,2- [2- (dimethylamino) ethyoxyl] ethanol,PENTROL,1- aziridine ethanol,1- crassitudes,1- butyl pyrrolidines,1- pyrrolidines (pyrrolidino) -1- cyclopentene,1- pyrrolidines -1- cyclohexene,1- (2- hydroxyethyls) pyrrolidines,3- pyrrolidines -1,2- propane diols,1- methyl -3- pyrrolidinols,1- ethyl -3- pyrrolidinols,1- methyl -2- pyrrolidine carbinols,2- methyl isophthalic acids-pyrrolin,1- methyl piperidines,1- ethyl piperidines,Dipiperidinomethane,1- ethyl piperidines,1,1 '-di-2-ethylhexylphosphine oxide (3- methyl piperidines),4,4 '-trimethylene is double (1- methyl piperidines),1,2,2,6,6- pentamethvls,1- piperidines diethylacetals,1- piperidine ethanols,3- piperidyls -1,2- propane diols,3- hydroxyl -1- methyl piperidines,1- ethyl -3- hydroxy piperidines,1- methyl -3- piperidine carbinols,4,4 '-trimethylene is double (1- piperidine ethanols),N,N '-bis- (2,2,6,6- tetramethyl -4- piperidyls) -1,6- hexamethylene diamines,1,2,3,6- tetrahydropyridines,1,4- lupetazins,4- (dimethylamino) -1,2,2,6,6- pentamethyl piperazines,1,Double (2- hydroxyethyls) piperazines of 4-,1,3,5- tetramethyls hexahydro -1,3,5- triazines,1,3,5- tetraethyls hexahydro -1,3,5- triazines,1,4,7- trimethyls -1,4,7- 7-triazacyclononanes,1,5,9- trimethyls -1,5,9- triazododecanes,1,4,8,11- tetramethyls -1,4,8,11- tetraazacyclododecane tetradecanes,1,4,7,10,13,16- vegolysens,4,7,10,13,16- hexanitrogen heterocycle octadecanes,TROPANE,QUINULIDINE,3-QUINULIDINOL,1,4- diazabicyclos [2.2.2] octane,Hexa,4- methyl morpholines,4- ethyl morpholines,4- (1- cyclopentene -1- bases) morpholine,1- morpholino -1- cyclohexene,1- morpholino -1- cycloheptenes,4- (2- hydroxyethyls) morpholine,3- morpholinoes -1,2- propane diols,4- [2- (dimethylamino) ethyl] morpholine,5- ethyl -1- azepines -3,Bicyclic [3.3.0] octane of 7- dioxas,1- azepines -3,Bicyclic [3.3.0] octane -5- methanol of 7- dioxas,4,7,13,The oxa-s -1 of 18- tetra-,10- diazabicyclos [8.5.5] icosane,4,7,13,16,The oxa-s -1 of 21- five,10- diazabicyclos [8.8.5] tricosane,4,7,13,16,21,The oxa-s -1 of 24- six,10- diazabicyclos [8.8.8] hexacosane,N,Accelerine,N- ethyl-N-methylanilines,N,N- diethylanilines,N,N- dibutyl anilines,1- Phenylpiperidines,Triphenylamine,N- Benzyl-N-ethyl aniline,2- (N-ethylaniline base) ethanol,N- phenyldiethanol-amines,N- (ethoxyethyl group)-methylphenylamine,N,N- dimethyl ortho-aminotoluenes,N,N- dimethyl meta-aminotoluenes,N,N- dimethyl-p-toluidines,N,N- diethyl-o-toluidines,N,N- diethyl-m-toluidines,N,N- diethyl-p-tlouidines,3- Dimethylaminophenols,3- diethylamino phenol,2- (toluidino between N- ethyls) ethanol,The 4- tert-butyl groups-N,Accelerine,The bromo- N of 4-,Accelerine,2,2 '-(to Tolylimino) dimethanols,4- (dimethylamino) benzyl carbinol,N,N,N’,N '-tetramethyl benzidine,N,N '-diglycidyl -4- glycidyloxyanilines,2,6- diisopropyls-N,Accelerine,The bromo- N of 4-,N- dimethyl -3- (trifluoromethyl) aniline,N,N,3,5- tetramethyl aniline,N,N,2,4,6- pentamethylaminobenzenes,4,4 '-di-2-ethylhexylphosphine oxide (2,6- diisopropyls-N,Accelerine),2,6- di-t-butyls -4- (dimethylaminomethyl) phenol,N,N,N’,N '-tetramethyl -1,4- phenylenediamines,4,4 '-di-2-ethylhexylphosphine oxide (N,Accelerine),4,4 '-di-2-ethylhexylphosphine oxide (N,N- diglycidylanilines),4,Double (the N of 4 '-ethenylidene,Accelerine),Concealed malachite green (the Application of ロ イ U マ ラ カ イ ト グ リ mono-,Leucomalachite green),4,4 '-bis- (dimethylamino) benzhydrol (Le of ベ Application ジ De ロ mono-,benzhydro),1,Double (dimethylamino) naphthalenes of 8-,2- (dimethylamino) fluorenes,N,N- dimethyl -1- phenyl ethylamines,3- (N- Benzyl-N-methylaminos) -1,2- propane diols,N,N- dimethyl benzylamines,N,N,N’,N '-tetrabenzyl methane diamines,N- methyldiphenyl base vinylamines,Tribenzylamine,N- (2- chloroethyls) dibenzylamine,N- Benzyl-N-methyl monoethanolamines,3- dibenzyl amino -1- propyl alcohol,2- dibenzyl amino -3- phenyl-1-propanols,N- ethyls -3,3 '-diphenyldipropylamine,3- methoxyl groups-N,N- dimethyl benzylamines,The bromo- N of 4-,N- diisopropyl benzylamines,1- (diphenyl methyl) azetidine,1- benzyl -3- pyrrolins,1- benzyl -3- pyrrolidinols,1- benzyl -2- pyrrolidine carbinols,1-(3,4- dihydro -2- naphthyls) pyrrolidines,1- methyl 4-phenyls -1,2,3,6- tetrahydropyridines,4- diphenylmethyls Oxy-1-methyl piperazine,1- benzyl -4- hydroxyl piperazines,1,3,5- tribenzyls hexahydro -1,3,5- triazines,4- phenylmorpholines,2,5- dimethyl -4- (morpholinomethyl) phenol,N,N '-dibenzyl -1,4,10,The oxa-s -7 of 13- tetra-,16- diazacyclo octadecanes,2- methylene -1,3,3- tri-methyl indoles are expired,JULODINE,8- hydroxyls JULODINE,5,10- dihydros -5,10- dimethylphenazines,10 methyl phenothiazine,TROGER ' S BASE or 5,6- benzos -4,7,13,16,21,The oxa-s -1 of 24- six,10- diazabicyclos [8.8.8] 26 alkane etc..
It is used as the above-mentioned amine that can be used,N- methyl ethylenediamines can also be included,NEED,N- propyl group ethylenediamines,N- isopropyl ethylenediamines,N,N- dimethyl-ethylenediamines,N,N- diethyl ethylenediamines,N,N- dibutyl ethylenediamines,N,N,N '-trimethyl ethylenediamine,N,N- dimethyl-N '-ethylethylenediamine,N,N- diethyl-N '-methyl ethylenediamine,N,N,N '-triethylethylenediamine,N- methyl isophthalic acids,3- propane diamine,N- ethyls -1,3- propane diamine,N- propyl group -1,3- propane diamine,N- isopropyls -1,3- propane diamine,3- dimethylamino propylamines,3- diethyl amino propylamines,3- dibutyl amino propyl amines,N,N,N '-trimethyl -1,3- propane diamine,N,N,2,2- tetraethyls -1,3- propane diamine,2- amino -5- diethylaminopentanes,Diethylenetriamines,N1- isopropyl diethylenetriamines,N,N,N’,N '-tetraethyl diethylenetriamines,N- (2- amino-ethyls) -1,3- propane diamine,3,3 '-diamino-N-methyl-di-n-propylamine,N- (3- aminopropyls) -1,3- propane diamine,3,Double (the N of 3 '-imino group,N- dimethyl propylamines),SPERMIDINE,Double (hexa-methylene) triamines,N,N’,Double (hexa-methylene) triamines of N "-trimethyl,4- (amino methyl) -1,8- octamethylenediamines,Trien,1,1,4,7,10,10- hexamethyl triens,N,N '-bis- (3- aminopropyls) ethylenediamine,N,N '-bis- (2- amino-ethyls) -1,3- propane diamine,N,N '-bis- (3- aminopropyls) -1,3- propane diamine,SPERMINE,Three (2- amino-ethyls) amine,Tetren,Penten,N- cyclohexyl -1,3- propane diamine,2- (2- aminoethylaminos) ethanol,1- (2- amino-ethyls) pyrrolidines,2- (2- amino-ethyls) -1- crassitudes,1- (2- pyrrolidinylmethyls) pyrrolidines,4- (1- pyrrolidinyls) piperidines,4- piperidinyl piperidines,1- (2- amino-ethyls) piperidines,1- (3- aminopropyls) -2- methyl sends coline,3- amino piperidines,1- methyl -4- (methylamino) piperidines,4- (amino-ethyl) piperidines,3- (4- aminobutyls) piperidines,4- amino -2,2,6,6- tetramethyl piperidines,4- dimethylaminos -2,2,6,6- tetramethyl piperidines,2- methyl -2- imidazolines,4,4- dimethyl -2- imidazolines,1- methyl piperazines,1- ethyl piperazidines,1- (2- hydroxyethyls) piperazine,1- [2- (2- hydroxyl-oxethyls) ethyl] piperazine,1- (2- amino-ethyls) piperazine,1,Double (3- aminopropyls) piperazines of 4-,HEXETIDIEN,1,4,5,6- tetrahydropyrimidines,1- methylhomopiperazins,3- amino kynurenins,1,Carbon -7- the alkene of 8- diazabicyclos [5.4.0] 11,1,3,4,6,7,8- hexahydro -2H- pyrimidos [1,2-A] pyrimidine,1,3,4,6,7,8- hexahydro -1- methyl -2H- pyrimidos [1,2-A] pyrimidine,4- (2- amino-ethyls) morpholine,4- (3- aminopropyls) morpholine,5,6- dihydro -2- isopropenyls -4,4,6- trimethyls -4H-1,3- oxazines,N- methyl isophthalic acids,2- phenylenediamines,N- phenyl -1,2- phenylenediamines,N,N- dimethyl -1,3- phenylenediamines,N,N- dimethyl -1,4- phenylenediamines,N,N- diethyl -1,4- phenylenediamines,N4,N4- diethyl -2- methyl isophthalic acids,4- phenylenediamines,2- methoxyl group-N4- phenyl -1,4- phenylenediamines,N- phenyl -1,4- phenylenediamines,N- methyl -4,4 '-methylene dianiline (MDA),N- phenylethylenediamines,N '-benzyl-N,N- dimethyl-ethylenediamines,N,N’,N "-tribenzyl three (2- amino-ethyls) amine,4- (hexadecylamino) benzylamine,4- dimethylaminobenzylamines,4- amino -1- benzyl diethylenediamines,2- phenyl -2- imidazolines,Tolazoline,2- (1- naphthyl methyls) -2- imidazolines,Fragrant appropriate amine,2,3- diphenyl -1,4- diaza spiros [4.5] decyl- 1,3- diene,4- benzyl -2- methyl -2- oxazolines,4,4- dimethyl -2- phenyl -2- oxazolines,4- methoxy -2- methyl -5- phenyl -2- oxazolines,2- methyl -5- phenyl -2- oxazoline -4- methanol,2,2 '-bis- [(4S) -4- benzyl -2- oxazolines],2,2 '-bis- [(4S) -4- phenyl -2- oxazolines],2,2 '-isopropylidene is double [(4S) -4- phenyl -2- oxazolines],2,2 '-di-2-ethylhexylphosphine oxide [(4R,5S)-4,5- diphenyl -2- oxazolines],Tetramisole,1-php,5- phenyl -1,4,5,6- tetrahydropyrimidines,1- benzyl diethylenediamines,1- cinnamoyl piperazines,1- toluoyl base piperazines,1-(2,3- xylyls) piperazine,1- (2- methoxyl groups) piperazine,1- (4- methoxyl groups) piperazine,1- (2- ethyoxyls) piperazine,4- morpholino aniline,Fomocaine (ホ モ カ イ Application,fomocaine),Polyethyleneimine,Or poly- (methyl) alkyl acrylate copolymer of grafting polyethylene imine etc. is combined with primary amino radical in a molecule,Amines etc. formed by secondary amino group and tertiary amino.
In addition, as above-mentioned amine, nitra-amine, commercially available modified amine, modified polyamine can also be used.As above-mentioned nitra-amine, 2- nitroanilines, 3- nitroanilines, 4- nitroanilines or 1- (4- nitrobenzophenones) piperazine etc. can be included.
As above-mentioned quaternary ammonium hydroxide, it can enumerate for example：TMAH salt, tetraethyl ammonium hydroxide salt, TPAOH salt, TBAH salt, triethyl methyl ammonium hydroxide salt, cetyltrimethylammonium hydroxide salt or benzyltrimethylammonium hydroxide salt etc..
As above-mentioned hydrazine compound, it can enumerate for example：Phenylhydrazine, 1,1- hydrazo-benzene, 1,2- hydrazo-benzene, 1- methyl isophthalic acids-phenylhydrazine or o-tolyl hydrazine etc..
As above-mentioned amide compound, it can enumerate for example：Malonamide, succinamide, fumaramide, adipamide, NIPECITANIDE, (methyl) alkyl acrylate-(methyl) acrylamide copolymer, styrene-(methyl) alkyl acrylate-(methyl) acrylamide copolymer, (methyl) alkyl acrylate-(methyl) acryloyl morpholine copolymer or styrene-(methyl) alkyl acrylate-(methyl) acryloyl morpholine copolymer etc..
As above-mentioned sulfhydryl compound, it can enumerate for example：1,2- dithioglycol, 1,3- dimercaptopropanes, 1,4- succinimide mercaptans, 1,5- pentane disulfide thioalcohols, 1,6- ethanthiols, 1, pungent two mercaptan of 8-, the mercaptan of 1,9- nonyls two, 2- mercaptoethyls ether, 1,2- diphenyl disulfides phenol, 1,3- diphenyl disulfides phenol, Isosorbide-5-Nitrae-diphenyl disulfide phenol, 1,2- benzene dimethanethiols, 1,3- benzene dimethanethiols, 1,4- benzene dimethanethiols or 4,4 '-sulphur biphenyl thiophenol (4,4 '-thiobenzenethiol) etc..
As above-mentioned sulfide compound, it can enumerate for example：Ethylene dithiol ether, methyl propyl disulfide, isopropyl disulfide or phenyl disulfide etc..
As above-mentioned phosphine compound, it can enumerate for example：Di-t-butyl phosphine, trimethyl-phosphine, 1, double (solutions of dimethyl phosphoryl) ethane of 2-, triethyl phosphine, tripropyl phosphine, tri isopropyl phosphine, tri isobutyl phosphine, tri-butyl phosphine, tri octyl phosphine, tricyclohexyl phosphine, 1, double (dicyclohexyl phosphinylidyne) butane of 4-, Phenylphosphine, diphenylphosphine, triphenylphosphine, 1, double (diphenylphosphoryl) ethane of 2-, dimethylphenylphosphine, diethyl phenyl phosphine, diallyl Phenylphosphine, methyldiphenyl base phosphine, ethyldiphenylphosphine, diphenyl propyl phosphine, isopropyl diphenyl base phosphine, diphenylacetylene phosphine, allyldiphenylphosphine, dicyclohexlphenylphosphine, tribenzyl phosphine, tri-o-tolyl phosphine, three tolylphosphines, three p-methylphenyl phosphines, three (2, 4, 6- trimethylphenyls) phosphine, double (diphenyl phosphinylidyne) methane, 1, double (diphenyl phosphinylidyne) ethane of 2-, 1, double (diphenyl phosphinylidyne) propane of 3-, 1, double (diphenyl phosphinylidyne) butane of 4-, or 2, 2 '-bis- (diphenyl phosphinylidynes) -1, 1 '-naphthalene etc..
It is preferred that above-mentioned alkali compounds (a2) is amine.During using amine, curability compound (B) solidification can be more promptly carried out.
As above-mentioned alkali compounds (a2) amine, at least there are 2 amino preferably in a molecule.At this point it is possible to more promptly carry out the solidification of curability compound (B).
As above-mentioned alkali compounds (a2) amine, the amine that preferably any one chemical formula in following formula (2)~(7) is represented.At this point it is possible to more promptly carry out the solidification of curability compound (B).
[chemical formula 22]
Figure GPA00001022289300191
[chemical formula 23]
Figure GPA00001022289300192
[chemical formula 24]
(CH3)4N+OH-   (4)
[chemical formula 25]
Figure GPA00001022289300193
In above-mentioned formula (5), R1Represent the alkylidene that carbon number is 1~10.
[chemical formula 26]
H2N-R2-NH2    (6)
In above-mentioned formula (6), R2Represent the alkylidene that carbon number is 1~10.
[chemical formula 27]
Figure GPA00001022289300201
(curability compound (B))
In the present invention, above-mentioned Photobase generator (A) is applied in combination with the curability compound (B) at least having 2 functional groups being selected from epoxy radicals, (methyl) acryloyl group, NCO, anhydride group and alkoxysilyl in a molecule.At least the curability compound (B) with 2 functional groups is effectively activated by the alkali produced by above-mentioned Photobase generator (A) in these molecule, so as to promptly solidify.Curability compound (B) can be used alone, and can also combine two or more and use.
It should be noted that in this manual, so-called " (methyl) acryloyl group " refers to the meaning of acryloyl group and methylacryloyl.In addition, so-called " (methyl) acrylic ", refers to the meaning of acrylic and methacrylic acid group.In addition, so-called " (methyl) acrylate ", refers to the meaning of acrylate and methacrylate.
It is preferred that above-mentioned curability compound (B) is the compound with epoxy radicals or NCO.During using these preferred compounds, the performance balance of curability and adaptation and cementability of the solidfied material on substrate is easily obtained.Wherein, particularly preferably using the carbamate prepolymer with NCO.During using carbamate prepolymer with NCO, it is easier to obtain the performance balance of curability and adaptation and cementability of the solidfied material on substrate.
As the curability compound (B) at least in said one molecule with 2 (methyl) acryloyl groups, it can enumerate for example：Compound with NCO passes through urethane acrylate class obtained from reaction etc. with (methyl) acrylic monomers with active hydrogen, compound with multiple epoxy radicals is with (methyl) acrylic acid or (methyl) acrylic monomer with hydroxyl passes through epoxy ester compounds class obtained from reaction etc., polyester acrylic esters, aklylene glycol two (methyl) esters of acrylic acid, PAG two (methyl) esters of acrylic acid, polyalcohol (methyl) esters of acrylic acid, silicone acrylates class, polybutadiene acrylic acid esters, biphenol A ethylene oxide adduct dimethylacrylate, trimethylolpropane PO is modified trimethyl acrylic ester or trimethylolpropane EO is modified trimethyl acrylic ester class etc..
As above-mentioned aklylene glycol two (methyl) esters of acrylic acid, ethylene glycol dimethacrylate, BDO dimethylacrylate, HDDMA or 1,9- nonanediol dimethylacrylate etc. can be included.
As above-mentioned PAG two (methyl) esters of acrylic acid, polyethylene glycol two (methyl) acrylate, (methyl) acrylate of polypropylene glycol two or polytetramethylene glycol two (methyl) acrylate etc. can be included.
As above-mentioned polyalcohol (methyl) esters of acrylic acid, glycerine two (methyl) acrylate, glycerine three (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, two (trimethylolpropane) tetraacrylates, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, Dipentaerythritol Pentaacrylate or dipentaerythritol acrylate etc. can be included.
As the above-mentioned curability compound (B) at least with 2 NCOs, it can enumerate for example：Tetramethylene diisocyanate, hexamethylene diisocyanate, eight methylene diisocyanates, ten dimethylene diisocyanates, 1,5- diisocyanate -2- methylpentanes, 1,3- double (isocyanatomethyl) hexamethylenes, Isosorbide-5-Nitrae-cyclohexene diisocyanate, 4,4 '-di-2-ethylhexylphosphine oxide (cyclohexyl isocyanate), IPDI, 1,3- phenylene diisocyanate, Isosorbide-5-Nitrae-phenylene diisocyanate, Toluene-2,4-diisocyanate, 4- diisocyanate, Toluene-2,4-diisocyanate, 6- diisocyanate, the phenyl isocyanate of 1- chloromethyls -2,4- bis-, 4,4 '-di-2-ethylhexylphosphine oxide (2,6- diethylbenzene based isocyanate), 4,4 '-di-2-ethylhexylphosphine oxide (phenyl isocyanate), 4,4 '-oxygen connection is double (phenyl isocyanate), 1,5- naphthalene diisocyanate, styrene -3- (methyl) acryloxypropyl isocyanate copolymer, (methyl) alkyl acrylate -3- (methyl) acryloxypropyl isocyanate copolymer, styrene-(methyl) alkyl acrylate -3- (methyl) acryloxypropyl isocyanate copolymers or carbamate prepolymer etc..
As the preparation method of above-mentioned carbamate prepolymer, following method can be enumerated, for example, polyol and above-mentioned polyisocyanate compound are mixed, the method for 3~5 hours or so is reacted at a temperature of 80~100 DEG C or so in stream of nitrogen gas.It is preferred that under conditions of the ratio (NCO/OH) for the hydroxyl (OH) that the NCO (NCO) that polyisocyanate compound has and above-mentioned polyol have is using equivalent ratio as 1.2~15 ratio, above-mentioned polyol is mixed with above-mentioned polyisocyanate compound.It is preferred that in the range of above-mentioned ratio (NCO/OH) is using equivalent ratio as 3~12.
When above-mentioned NCO/OH equivalent proportion is less than 1.2, the viscosity of resulting carbamate prepolymer becomes too high, is difficult to use Photocurable composition as bonding agent sometimes.When above-mentioned NCO/OH equivalent proportion is more than 15, Photocurable composition is easily foamed in solidification, the cohesiveness reduction of solidfied material, and sufficient adhesive strength can not be obtained sometimes.
As the above-mentioned curability compound (B) in a molecule at least with 2 anhydride groups, it can enumerate for example：Bicyclic [2, 2, 2] octyl- 7- alkene -2, 3, 5, 6- tetracarboxylic dianhydrides, ethylenediamine tetra-acetic acid dianhydride, diethylene-triamine pentaacetic acid dianhydride, 3, 3 ', 4, 4 '-benzophenone tetracarboxylic dianhydride, 4, 4 '-(hexafluoroisopropyli,ene) diphthalic anhydrides, 1, 2, 4, 5- benzene tertacarbonic acid's dianhydrides, 1, 4, 5, 8- naphthalene tetracarboxylic acid dianhydrides, 3, 4, 9, 10- perylenetetracarboxylic dianhydrides, pyromellitic dianhydride, styrene-maleic anhydride copolymer, (methyl) alkyl acrylate-copolymer-maleic anhydride, styrene-(methyl) alkyl acrylate-copolymer-maleic anhydride, tetracarboxylic dianhydride and the reaction product of diamines, or the reaction product of tetracarboxylic dianhydride and dihydric alcohol etc..
As the curability compound (B) at least in said one molecule with 2 alkoxysilyls, it can enumerate for example：Tetramethoxy-silicane,Tetraethoxysilane,Tetraisopropoxysilan,Trimethoxy silane,MTMS,Triethoxysilane,Ethyl triethoxysilane,Dimethoxydimethylsilane,Cyclohexyl dimethoxymethylsilane,Di ethoxy di methyl-monosilane,Dimethoxy-methyl octyl group silane,Diethoxymethylvinylschane,Chloromethyl (diisopropoxy) methyl-monosilane,Dimethoxymethylphenylsilane,Diethoxy diphenyl silane,Trimethoxy propyl silane,Trimethoxysilane,Octyl group trimethoxy silane,Octadecyl trimethoxysilane,MTES,Isobutyl triethoxy silane,Octyltri-ethoxysilane,Vinyltrimethoxy silane,VTES,Allyltriethoxysilane,(3- chloropropyls) trimethoxy silane,Chloromethyl triethoxysilane,Three (2- methoxy ethoxies) vinyl silanes,3- glycidoxypropyltrime,hoxysilanes,Diethoxy (3- glycidoxypropyl groups) methyl-monosilane,Trimethoxy [2- (7- oxabicyclos [4.1.0] hept- 3- yls) ethyl] silane,One chlorine trimethoxy silane,One chlorine triethoxysilane,One chlorine three (1,3- dimethyl butyrates epoxide) silane,Dichlorodiethyl TMOS,3- (triethoxysilyl) propionitrile,4- (triethoxysilyl) butyronitrile,3- (triethoxysilyl) propylisocyanate,3- (triethoxysilyl) propyl dithiocarbamate isocyanates,Phenyltrimethoxysila,e,Phenyl triethoxysilane,Tetrapropoxysilane,Four butoxy silanes,1,3,5,7- tetraethoxies -1,3,5,7- tetramethyl-ring tetrasiloxanes,1,3,5,7- tetramethyls -1,3,5,The propoxyl group cyclotetrasiloxanes of 7- tetra-,1,3,5,7- tetraisopropoxides -1,3,5,7- tetramethyl-ring tetrasiloxanes,1,3,5,The butoxy -1 of 7- tetra-,3,5,7- tetramethyl-ring tetrasiloxanes,1,3,5,7,The ethyoxyls -1 of 9- five,3,5,7,9- pentamethyl D5s,Octamethylcy-clotetrasiloxane,Decamethylcyclopentaandoxane,The siloxanes of ten diformazan basic ring six,Hexaphenyl cyclotrisiloxane,Octaphenylcyclotetrasiloxane,1,3,5,7- tetramethyl-ring tetrasiloxanes,1,3,5,7- tetramethyls -1,3,5,7- tetraphenyl cyclotetrasiloxanes,1,1,3,3,5,The silazane of 5- pregnancy basic ring three,1,1,3,3,5,5,7,7- octamethylcyclotetrasilazanes,1,7- diacetoxy octamethylcyclotetrasiloxanes,1,7- dichlorooctamethyltetrasiloxanes,1,1,3,3,5,5- vegolysens,5- dichloro trisiloxanes,1,3- dichloro tetra isopropyl disiloxanes,1,3- diethoxy tetramethyl disiloxanes,1,3- dimethoxy tetramethyl disiloxanes,1,1,3,3- tetramethyls -1,3- dichloro disiloxane,1,Double (methyl dichloro silicyl) ethane of 2-,Diacetoxy diphenyl silane,Methyl three (ethyl methyl ketone oximido) silane,(the N of methyl three,N- diethyl aminos epoxide) silane,Double (ethyl methyl ketone oximido) methyl isopropyl TMOSs,Double (ethyl methyl ketone oximido) (ethoxymethyl) base silanes,2-(3,4- epoxycyclohexylethyls) trimethyl silane,Three (1- ethylene methacrylics epoxide) vinyl silanes,The iso-propenyloxysilane of methyl three,Ethyltriacetoxysilane,Methyl triacetoxysilane,Diacetoxy dimethylsilane,Triacetoxyl group vinyl silanes,Four acetoxylsilanes,Diacetoxy aminomethyl phenyl silane,Dimethoxy-ethyl MIBK oximido methyl-monosilane,Double (trimethoxysilyl) benzene,Double (triethoxysilyl) benzene,Three (trimethoxysilyl) benzene,Three (triethoxysilyl) benzene,Double (trimethoxysilyl) biphenyl,Double (triethoxysilyl) biphenyl,Three (trimethoxysilyl) biphenyl,Three (triethoxysilyl) biphenyl,Double (trimethoxysilyl) naphthalenes,Double (triethoxysilyl) naphthalenes,Three (trimethoxysilyl) naphthalenes,Three (triethoxysilyl) naphthalenes,Double (methyl dimethoxy epoxide silicyl) benzene,Double (methyl diethoxy silicyl) benzene,Three (methyl dimethoxy epoxide silicyl) benzene,Three (methyl diethoxy silicyl) benzene,Double (methyl dimethoxy epoxide silicyl) biphenyl,Double (methyl diethoxy silicyl) biphenyl,Three (methyl dimethoxy epoxide silicyl) biphenyl,Three (methyl diethoxy silicyl) biphenyl,Double (methyl dimethoxy epoxide silicyl) naphthalenes,Double (methyl diethoxy silicyl) naphthalenes,Three (methyl dimethoxy epoxide silicyl) naphthalenes,Three (methyl diethoxy silicyl) naphthalenes,Three (dimethylmethoxysilylgroups groups) benzene,Three (dimethylmethoxysilylgroups groups) biphenyl,Three (dimethylmethoxysilylgroups groups) naphthalenes,Double (trimethoxysilyl acetenyl) benzene,Double (methyl diethoxy silylethynyl) benzene,Three (trimethoxysilyl acetenyl) benzene,Three (methyl dimethoxy epoxide silylethynyl) benzene,Double (trimethoxy-silylpropyl) benzene,Double (methyl diethoxy silylpropyl) benzene,Three (trimethoxy-silylpropyl) benzene,Three (methyl dimethoxy epoxide silylpropyl) benzene,Double (trimethoxysilyl) methane,Double (methyl dimethoxy epoxide silicyl) methane,Double (trimethoxysilyl) ethane,Double (methyl dimethoxy epoxide silicyl) ethane,Double (trimethoxysilyl) propane,Double (methyl dimethoxy epoxide silicyl) propane,Double (trimethoxysilyl) butane,Double (methyl dimethoxy epoxide silicyl) butane,Double (trimethoxysilyl) pentanes,Double (methyl dimethoxy epoxide silicyl) pentanes,Double (trimethoxysilyl) hexanes,Double (methyl dimethoxy epoxide silicyl) hexanes,Double (trimethoxysilyl) heptane,Double (methyl dimethoxy epoxide silicyl) heptane,Double (trimethoxysilyl) octanes,Double (methyl dimethoxy epoxide silicyl) octanes,Double (trimethoxy-silylpropyl) amine,Double (methyl dimethoxy epoxide silylpropyl) amine,Double (trimethoxy-silylpropyl) ethylenediamines,Double (methyl dimethoxy epoxide silylpropyl) ethylenediamines,Three (trimethoxy-silylpropyl) isocyanuric acid esters,Hexa methoxy disilane,Methyl dimethoxy epoxide disilane,Six ethyoxyl disilane,Methyl diethoxy disilane,Dimethoxy tetramethyl disiloxane,Trimethoxy trimethyldisiloxane,Tetramethoxy dimethyldisiloxane,Pentamethoxyl tetramethyldisiloxane,Hexa methoxy disiloxane,Dimethoxy hexam ethylcyclotrisiloxane,Trimethoxy pentamethyl trisiloxanes,Tetramethoxy tetramethyl trisiloxanes,Pentamethoxyl trimethyl trisiloxanes,Hexa methoxy dimethyl trisiloxanes,Seven methoxy trisiloxanes,Eight methoxyl group trisiloxanes,1,3,5,7- tetramethoxies -1,3,5,7- tetramethyl-ring tetrasiloxanes,Eight methoxyl group cyclotetrasiloxanes,1,3,5,7- tetraethoxies -1,3,5,7- tetramethyl-ring tetrasiloxanes,Eight ethyoxyl cyclotetrasiloxanes,Eight (trimethoxysilyl acetenyl)-T8- silsesquioxanes (オ キ タ キ ス (ト リ メ ト キ シ シ リ Le エ チ ニ Le)-T8- シ Le セ キ ス オ キ サ Application),Eight (methyl dimethoxy epoxide silylethynyl)-T8- silsesquioxanes,Eight (dimethylmethoxysilylgroups groups acetenyl)-T8- silsesquioxanes,Double (methyl dimethoxy epoxide silicyl) polypropylene glycols,Double (trimethoxysilyl) polypropylene glycols,Double (methyl dimethoxy epoxide silicyl) polyisobutene,(methyl) acrylate containing alkoxysilyl,Styrene -3- (trimethoxysilyl) propyl group (methyl) acrylate copolymer,(methyl) alkyl acrylate -3- (trimethoxysilyl) propyl group (methyl) Acrylate-styrene bipolymer-(methyl) alkyl acrylate -3- (trimethoxysilyl) propyl group (methyl) acrylate copolymer,Styrene -3- (methyl dimethoxy epoxide silicyl) propyl group (methyl) acrylate copolymer,(methyl) alkyl acrylate -3- (methyl dimethoxy epoxide silicyl) propyl group (methyl) Acrylate-styrene bipolymer-(methyl) alkyl acrylate -3- (methyl dimethoxy epoxide silicyl) propyl group (methyl) acrylate copolymer etc..
It is above-mentioned that at least the curability compound (B) with 2 epoxy radicals is not particularly limited in a molecule.As the above-mentioned curability compound (B) in a molecule at least with 2 epoxy radicals, it can enumerate for example：Glycidyl ether type epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, alicyclic epoxy resin, epoxidized SBS or epoxidized butadiene etc..Wherein, preferably use selected from least one of glycidyl ether type epoxy resin, glycidyl ester epoxy resin and glycidyl amine epoxy resin.During using these preferred curability compounds, by making the curability compound effectively activate as the alkali produced by above-mentioned Photobase generator (A), so as to promptly solidify.
As above-mentioned glycidyl ether type epoxy resin, it can enumerate for example：Biphenol A types epoxy resin, biphenol F types epoxy resin, biphenol S types epoxy resin, hydrogenation biphenol A types epoxy resin, hydrogenation biphenol F types epoxy resin, hydrogenation biphenol S types epoxy resin, phenol novolak type epoxy resin, brominated phenol phenolic resin varnish type epoxy resin, 1,1,2,2- tetra- (4- glycidol oxygen phenyl) ethane, trihydroxymethylpropanyltri diglycidyl ether, neopentylglycol diglycidyl ether, polypropylene glycol diglycidyl ether, polyethyleneglycol diglycidylether or BDDE etc..
As above-mentioned glycidyl ester epoxy resin, it can enumerate for example：Hexamethylene -1,2- dicarboxylic acids 2-glycidyl ester, 1,2,3,6- tetrahydrophthalic acid 2-glycidyl esters, o-phthalic acid diglycidyl ester or 1,2,3,6- tetrahydrochysene -4- methylphthalic acid 2-glycidyl esters etc..
As above-mentioned glycidyl amine epoxy resin, it can enumerate for example：4,4 '-di-2-ethylhexylphosphine oxide (N, N- diglycidylaniline), N, N- diglycidyl -2- glycidyloxyanilines, N, N- diglycidylanilines, 2- methyl-N, N- diglycidylaniline or N, N ', N "-triglycidyl group isocyanuric acid ester etc..
Relative to the above-mentioned curability compound (B) of 100 parts by weight, the content range of above-mentioned Photobase generator (A) is preferably 1~200 parts by weight, more preferably 10~150 parts by weight, more preferably 15~100 parts by weight, particularly preferably 20~80 parts by weight.
When the amount of Photobase generator (A) is very few, the alkali produced by irradiation light is very few, and curability compound (B) can not be cured sufficiently sometimes.When the amount of Photobase generator (A) is excessive, the alkali produced by irradiation light is excessive, the functional group reactionses of some alkali sometimes not with curability compound (B), and can not obtain the sufficient degree of cross linking sometimes.
In addition; relative to 1 mole of functional group's total amount being selected from curability compound (B) in epoxy radicals, (methyl) acryloyl group, NCO, anhydride group and alkoxysilyl, make the basic functionality of Photobase generator (A) alkali compounds (a2) produced when light is decomposed completely preferably in the range of 0.01~2 mole.
In curability compound (B) selected from epoxy radicals, (methyl) acryloyl group, NCO, anhydride group and functional group's total mole number and the mol ratio of the total mole number of the basic functionality of alkali compounds (a2) in alkoxysilyl preferably in the range of 1: 0.01~1: 2.
When the molal quantity of above-mentioned basic functionality is very few, the alkali produced by irradiation light is very few, and curability compound (B) fully solidification can not be made sometimes.When the molal quantity of basic functionality is excessive, the alkali produced by irradiation light is excessive, the functional group reactionses of some alkali sometimes not with curability compound (B), and can not obtain the sufficient degree of cross linking sometimes.
In addition; value (number of number-average molecular weight/functional group) (hereinafter also referred to as functional equivalent) obtained from the sum selected from epoxy radicals, (methyl) acryloyl group, NCO, anhydride group and the functional group in alkoxysilyl is preferably in the range of 170~50000 in the number-average molecular weight divided by curable compounds (B) of curability compound (B).When above-mentioned functional equivalent is less than 170, although curability compound (B) solidifies, but the easily functional group of remained unreacted.In addition, the crosslink density of solidfied material is significantly improved, therefore the cementability of Photocurable composition becomes unstable, and when being engaged by solidfied material with bonded body, the adhesive strength of solidfied material and bonded body can not be fully obtained sometimes.When above-mentioned functional equivalent is more than 50000, although curability compound (B) reacts, but is crosslinked sometimes insufficient.Now, it is possible to can not fully obtain the adhesive strength of solidfied material and bonded body.Above-mentioned functional equivalent is more preferably in the range of 180~20000, further preferably in the range of 250~10000.In addition, during using a variety of curability compound (B), above-mentioned functional equivalent is the average value calculated according to evaluation method described later.
(alkali multiplication agent (C))
The Photocurable composition of the present invention, which preferably further contains, makes the increased alkali multiplication agent (C) of growing amount of alkali by the effect of alkali.
As above-mentioned alkali multiplication agent (C), it can enumerate for example：Two functional-types, spherical multifunctional oligomeric, 9- fluorenyl carbamate derivatives of straight chain polymer type or silicone-type etc..
Above-mentioned 9- fluorenyls carbamate derivatives can for example be obtained by the addition reaction of 1,6- hexamethylene diisocyanates and isocyanate derivates.It is used as above-mentioned isocyanate derivates, such as m xylene diisocyanate, toluene di-isocyanate(TDI), IPDI, 1,6- hexylidene diisocyanates, 2- (methyl) acryloyloxyethyl isocyanates or copolymer containing 2- (methyl) acryloyloxyethyl isocyanate etc. can be enumerated.These 9- fluorenyl carbamate derivatives can be used alone, and can also combine two or more and use.
Above-mentioned alkali multiplication agent (C) preferably has the alkali multiplication agent (C1) of the alkali proliferative group of following formula (10) expression.
[chemical formula 28]
Figure GPA00001022289300261
The alkali multiplication agent (C1) of the alkali proliferative group represented with above-mentioned formula (10) is decomposed by alkali breeder reaction, regenerates amine.And then, produced amine plays a role as new catalyst, produces substantial amounts of new amine proliferative.The alkali proliferative group that the above-mentioned formula (10) existed in intramolecular is represented is more, more effectively can cause alkali breeder reaction in intramolecular, therefore, it can the formation efficiency for expecting to improve amino.
In the alkali breeder reaction of alkali multiplication agent (C1) of the alkali proliferative group represented with above-mentioned formula (10) has been used, active hydrogen atom is sloughed by the effect of alkali, carbanion is formed.Then, carbamic acid departs from, then is decomposed and generate amino and carbon dioxide.The amino accelerates the reaction as catalyst.Shown in for example following reaction equations (X1) of the reaction
[chemical formula 29]
Figure GPA00001022289300271
Formula (X1)
It is preferred that the alkali proliferative group that above-mentioned formula (10) represents is the alkali proliferative group that following formula (11) is represented.
[chemical formula 30]
Figure GPA00001022289300272
In above-mentioned formula (11), Z represents substituted or unsubstituted alkylidene.
In above-mentioned formula (11), as Z specific example, methylene, ethylidene or propylidene etc. can be enumerated.It is preferred that Z is unsubstituted alkylidene, because in this case can effectively cause above-mentioned alkali breeder reaction.Wherein, more preferably Z is methylene, because the steric hindrance now in Z reduces, it is easier to effectively cause alkali breeder reaction.
It is preferred that the alkali multiplication agent of the alkali proliferative group represented with above-mentioned formula (11) is the alkali multiplication agent that following formula (12) is represented.
[chemical formula 31]
Figure GPA00001022289300273
In above-mentioned formula (12), X represents hydrogen, substituted alkyl or unsubstituted alkyl, and Z represents substituted or unsubstituted alkylidene, and n represents 1~4 integer.
In above-mentioned formula (12), as X specific example, methyl, ethyl or propyl group etc. can be enumerated.It is preferred that X is unsubstituted alkyl, because in this case can effectively cause alkali breeder reaction.Wherein, more preferably X is ethyl, because the steric hindrance now in X reduces, it is easier to effectively cause alkali breeder reaction.
In above-mentioned formula (12), n represents 1~4 integer.When alkali multiplication agent represented by above-mentioned formula (12) has multiple 9- fluorenyls carbamate groups for same intramolecular, it is easier to effectively cause alkali breeder reaction under the catalytic action of produced alkali.Therefore, the n in above-mentioned formula (12) is preferably 3 or 4.
The specific example of the alkali multiplication agent represented as above-mentioned formula (12), can enumerate the alkali multiplication agent (Flu4) that the alkali multiplication agent (Flu3) or following formula (14) of following formula (13) expression are represented.The alkali multiplication agent that following formula (13) and formula (14) are represented can be obtained according to method described in No. 06/095670 pamphlet of International Publication No..
[chemical formula 32]
Figure GPA00001022289300281
[chemical formula 33]
Figure GPA00001022289300282
The alkali multiplication agent that above-mentioned formula (13) and formula (14) are represented has multiple 9- fluorenyls carbamate groups in same intramolecular respectively.Therefore, it is easier to effectively cause alkali breeder reaction under the catalytic action of produced alkali.More preferably alkali multiplication agent (C) is the alkali multiplication agent that above-mentioned formula (13) is represented, further preferred alkali multiplication agent (C) is the alkali multiplication agent that above-mentioned formula (14) is represented.During using these preferred alkali multiplication agents, the generation efficiency of alkali can be further improved.
The synthetic method respectively with the respective represented alkali multiplication agent of above-mentioned formula (10) and the alkali multiplication agent of the alkali proliferative group of (11) expression or above-mentioned formula (12)~(14) is not particularly limited.These alkali multiplication agents can be synthesized by the following method, for example, the addition reaction of the addition reaction of fluorenyl carbinol and isocyanate derivates, the acrylate monomer with fluorenyl carbamate groups and polysulfide 01 derivatives.Can be by being suitably easier to obtain alkali multiplication agent using tin catalyst in previous addition reaction；And can be by being suitably easier to obtain alkali multiplication agent using base catalyst in latter addition reaction.
The alkali proliferative group that further preferably above-mentioned formula (10) represents is the alkali proliferative group that following formula (15) is represented.
[chemical formula 34]
Figure GPA00001022289300291
In above-mentioned formula (15), R represents hydrogen or methyl.
The alkali multiplication agent (C1) more preferably with the alkali proliferative group of above-mentioned formula (10) expression is the alkali multiplication agent of the unsaturated group of alkali proliferative group and following formula (16) expression represented with above-mentioned formula (15).
[chemical formula 35]
In above-mentioned formula (16), R represents hydrogen or methyl.
The alkali multiplication agent for the unsaturated group that the alkali proliferative group and above-mentioned formula (16) represented with above-mentioned formula (15) is represented is chemically bonded by crosslinking with curability compound (B).Therefore, alkali multiplication agent is entered in solidfied material, so as to suppress because of residual alkali multiplication agent and caused by pollution.
The alkali multiplication agent of the alkali proliferative group represented with above-mentioned formula (15) can be obtained for example, by the compound of unsaturated group represented by following reaction equations (X2), being represented with above-mentioned formula (16) and the addition reaction of N- (2- mercaptoethyls) carbamic acid 9- fluorenyl methyl esters.It should be noted that in the addition reaction, the R in above-mentioned formula (15) is derived from the R in the unsaturated group that above-mentioned formula (16) is represented.
[chemical formula 36]
Figure GPA00001022289300293
Formula (X2)
In above-mentioned formula (X2), R represents hydrogen or methyl.
The compound of the unsaturated group represented with above-mentioned formula (16) is with (methyl) acrylate-based compound.
As the compound of the unsaturated group represented with above-mentioned formula (15), it can be used such as (methyl) acrylic ester monomer or oligomer.These《Photocuring technology handbook material》It is on the books in (TECHNONET Co., Ltd., 2000).
In the case that alkali multiplication agent is the alkali multiplication agent of the alkali proliferative group containing multiple above-mentioned formulas (15) expressions in same molecule, it will more effectively cause alkali breeder reaction.Therefore, it is easier to carry out epoxy compounds etc. and the cross-linking reaction of curability compound (B).It is therefore preferable that alkali multiplication agent (C) is at least to have 2 (methyl) acrylate-based monomer or oligomer.As such compound, it can use《Photocuring technology handbook material》Page 20~42 and page 60~68 record multi-functional (methyl) acrylate monomer or page 84~118 record (methyl) acrylate oligomer.
It is used as above-mentioned multi-functional (methyl) acrylate monomer or (methyl) acrylate oligomer,Specifically,Ethylene glycol two (methyl) acrylate can be enumerated,1,4- butanediols two (methyl) acrylate,1,6- hexylene glycols two (methyl) acrylate,Neopentyl glycol two (methyl) acrylate,Glycerine two (methyl) acrylate,Diethylene glycol two (methyl) acrylate,Triethylene glycol two (methyl) acrylate,Tetraethylene glycol two (methyl) acrylate,Polyethylene glycol two (methyl) acrylate,DPG two (methyl) acrylate,Tripropylene glycol two (methyl) acrylate,Cyclohexanedimethanol two (methyl) acrylate,Alkoxylate hexylene glycol two (methyl) acrylate,Alkoxylated cyclohexane dimethanol two (methyl) acrylate,Ethoxylated neopentylglycol two (methyl) acrylate,Two (methyl) acrylated isocyanuric acid esters,EO modified bisphenol As two (methyl) acrylate,Trimethylolpropane tris (methyl) acrylate,Ethoxylated trimethylolpropane three (methyl) acrylate,Propoxylation trimethylolpropane tris (methyl) acrylate,Pentaerythrite three (methyl) acrylate,Caprolactone modification trimethylolpropane tris (methyl) acrylate,EO is modified trimethylolpropane tris (methyl) acrylate,Three (acrylyl oxy-ethyl) isocyanuric acid esters,Pentaerythrite four (methyl) acrylate,Pentaerythrite ethyoxyl tetraacrylate,Dipentaerythritol five (methyl) acrylate,Dipentaerythritol six (methyl) acrylate,Caprolactone modification dipentaerythritol six (methyl) acrylate,Polyesters acrylate oligomer,Epoxy acrylate or carbamate (methyl) acrylate,Or their analog.
As above-mentioned multi-functional (methyl) acrylate monomer or (methyl) acrylate oligomer, multi-functional (methyl) acrylate described in compound, Unexamined Patent 11-193317 publications and the JP 2005-76005 publications of such as phenolic varnish type can also be used.These materials may be used singly or in combination of two or more.
The quantity for the alkali proliferative group that above-mentioned formula (15) in same molecule in order to increase alkali multiplication agent is represented, can use the compound for the unsaturated group that at least there are 2 above-mentioned formulas (16) to represent.
In order to obtain the compound for the unsaturated group that at least there are 2 above-mentioned formulas (16) to represent, for example, the compound of the unsaturated group represented with above-mentioned formula (16) and α-thioglycerin can be made to carry out Michael addition reaction.Thus, unsaturated group is converted into the group of the diol substituted of following formula (17) expression.Then, hydroxyl is esterified or urethane.As described later, by the reaction, for example, 1 unsaturated group can be converted into 2 or 4 unsaturated groups.
[chemical formula 37]
Figure GPA00001022289300311
In above-mentioned formula (17), R represents hydrogen or methyl.
When making the compound for the unsaturated group that at least there are 2 above-mentioned formulas (16) to represent with α-thioglycerin reaction, relative to 1 mole above-mentioned unsaturated group uses α-thioglycerin preferably in the range of 0.5~1.5 mole.When all unsaturated groups are converted into the group that above-mentioned formula (17) with diol structure is represented, relative to 1 mole above-mentioned unsaturated group preferably uses 1.0~1.2 moles of α-thioglycerin, more preferably using 1.0 moles of α-thioglycerins.In order to promote the reaction, base catalyst is preferably used.
As above-mentioned base catalyst, tertiary amine is preferably used.As above-mentioned base catalyst, it can enumerate for example：Triethylamine, tripropyl amine (TPA), tri-n-butylamine, dimethyl benzylamine, N methyldiethanol amine, pyridine, picoline or lutidines etc..As above-mentioned base catalyst, deacidite can also be used.
For the reaction temperature of the above-mentioned reaction of the compound for obtaining the unsaturated group that at least there are 2 above-mentioned formulas (16) to represent, the preferred scope of the scope, more preferably room temperature~100 DEG C of room temperature (23 DEG C)~150 DEG C.Reaction time can suitably change according to reaction temperature.Reaction time is preferably the scope of 10 minutes~60 hours, the scope of more preferably 1 hour~50 hours.
Imported as on the hydroxyl of the polyol compound of the group represented with above-mentioned formula (17) as (methyl) of unsaturated group acrylate-based method, esterification process or urethane method can be used.
For above-mentioned esterification process, (methyl) acryloyl chloride or (methyl) acrylic anhydride can be used, it is acrylate-based to import (methyl) according to usual way.As above-mentioned esterification process, method as shown in following reaction equations (X3), making the polyol compound carry out dehydration condensation with (methyl) acrylic acid in presence of an acid catalyst is preferably used.The water generated in the reaction can be removed by azeotropic etc..
[chemical formula 38]
Figure GPA00001022289300321
Formula (X3)
In above-mentioned reaction equation (X3), R represents hydrogen or methyl.
Above-mentioned urethane method uses the addition reaction of the polyol compound and (methyl) acrylate derivative with NCO.As the isocyanate compound used in the reaction, it can enumerate for example：(Showa electrician manufactures acrylic acid 2- isocyanatoethyls：KARENZ (カ レ Application ズ) AOI), methacrylic acid 2- isocyanatoethyls (Showa electrician manufacture：KARENZ MOI) or (the Showa electrician manufacture of the acryloxy -2- NCO -2- methylpropanes of 1,3- bis-：KARENZBEI) etc..
Relative to 1 hydroxy in the polyol compound of the base represented with above-mentioned formula (17), the usage amount of above-mentioned isocyanate compound is preferably 0.5~2.0 mole, more preferably 0.5~1.5 mole, more preferably 1.0~1.2 moles.
In order to promote above-mentioned addition reaction in the solvent for dissolving above-mentioned polyol compound at least in part, the base catalyst used in the above-mentioned addition reaction for diol substituted is preferably directly used in.Can be further using catalyst such as dibutyl tin laurates.In addition, in order to suppress polymerisation, preferably using polymerization inhibitor.Reaction temperature is preferably the scope of room temperature~100 DEG C, more preferably 40~80 DEG C.Reaction time can suitably change according to reaction temperature.Reaction time is preferably the scope of 30 minutes~20 hours, the scope of more preferably 1 hour~15 hours.
When reaction removes excessive isocyanate compound after terminating, for example, N can be added into reaction solution, N- dimethylethanolamines make it be reacted with excessive isocyanate compound.Then, acidic aqueous solution can be used to be washed or uses acid-exchange resin to be adsorbed.
In above-mentioned addition reaction, the hydroxyl formation amino-formate bond in the group that NCO is represented with above-mentioned formula (17).Therefore, when using (methyl) acrylic acid 2- isocyanatoethyls, such as shown in following reaction equations (X4), every 1 hydroxyl is imported into 1 unsaturated group.
[chemical formula 39]
Figure GPA00001022289300331
Formula (X4)
In above-mentioned reaction equation (X4), R represents hydrogen or methyl.
When using 1,3- bis- (methyl) acryloyl-oxy -2- NCO -2- methylpropanes, such as shown in following reaction equations (X5), every 1 hydroxyl is imported into 2 unsaturated groups.In above-mentioned reaction equation (X4), in the same manner as above-mentioned reaction equation (X3), the structure with 2 branches is obtained.It is acrylate-based due to importing 2 on 1 hydroxyl in following reaction equations (X5), therefore once obtain the structure with 4 branches.
[chemical formula 40]
Figure GPA00001022289300332
Formula (X5)
In above-mentioned reaction equation (X5), R represents hydrogen or methyl.
As shown in above-mentioned reaction equation (X3)~(X5), it is esterified or urethane by the hydroxyl in the group that represents above-mentioned formula (17), multiple unsaturated groups represented by above-mentioned formula (16) are reproduced.By making multiple unsaturated groups after regeneration further carry out addition reaction with α-thioglycerin, more hydroxyls can be imported.This means; the importing for importing (methyl) acryloyl group to hydroxyl after the Michael addition reaction and the addition reaction of unsaturated group and α-thioglycerin is repeated to react, the tree (dendrimer) equivalent to generation number can be manufactured.The tree that (methyl) acryloyl group has been imported in molecule chain end can be manufactured by respective reaction.It therefore, it can to obtain the compound that there is the unsaturated group that multiple above-mentioned formulas (16) represent in molecule chain end.
In order to which the unsaturated group for representing above-mentioned formula (16) is converted into the alkali proliferative group of above-mentioned formula (15) expression, it is preferred to use the compound of the unsaturated group represented with above-mentioned formula (16) and the addition reaction of N- (2- mercaptoethyls) carbamic acid 9- fluorenyl methyl esters.
Above-mentioned N- (2- mercaptoethyls) carbamic acid 9- fluorenyl methyl esters are because with sulfydryl, therefore easily, the compound of the unsaturated group with being represented with above-mentioned formula (16) carries out Michael addition reaction.It therefore, it can be readily available the compound of the alkali proliferative group represented with above-mentioned formula (15).
In the compound of unsaturated group represented with above-mentioned formula (16) and the reaction of N- (2- mercaptoethyls) carbamic acid 9- fluorenyl methyl esters, it during using the compound in same molecule with unsaturated group that the above-mentioned formula of at least two (16) represents, can react all unsaturated groups and sulfhydryl compound.Alternatively, it is also possible to make part unsaturated group be reacted with sulfhydryl compound.For having compound of the alkali proliferative group that above-mentioned formula (15) is represented with the unsaturated group of above-mentioned formula (16) expression in same molecule, the amino generated by alkali proliferative group carries out addition reaction with unsaturated group.Therefore, curing reaction can be achieved in the compound in same molecule with the alkali proliferative group and unsaturated group in itself.
The use ratio of unsaturated group and N- (2- mercaptoethyls) carbamic acid 9- fluorenyl methyl esters that above-mentioned formula (11) represents can suitably change according to the conversion ratio of unsaturated group.The unsaturated group represented relative to 1 mole of above-mentioned formula (11), preferably uses 1.0 moles~1.5 moles N- (2- mercaptoethyls) carbamic acid 9- fluorenyl methyl esters.In order that the reaction is efficiently carried out, base catalyst is preferably used.
For above-mentioned unsaturated group to be changed into the base catalyst of above-mentioned alkali proliferative group, preferably tertiary amine.As base catalyst, it can enumerate for example：Triethylamine, tripropyl amine (TPA), tri-n-butylamine, dimethyl benzylamine, N, N- diisopropyls methyl amine, N, N- dicyclohexylmethylamines, N methyldiethanol amine, pyridine, picoline, lutidines or deacidite etc..The reaction temperature that above-mentioned unsaturated group is changed into the reaction of above-mentioned alkali proliferative group is preferably the scope of the scope, more preferably room temperature~100 DEG C of room temperature~150 DEG C.Reaction time can suitably change according to reaction temperature.Reaction time is preferably the scope of 10 minutes~60 hours, the scope of more preferably 1 hour~50 hours.
Relative to the above-mentioned curability compound (B) of 100 parts by weight, the preferred content of above-mentioned alkali multiplication agent (C) is in the range of 20~100 parts by weight.When the amount of alkali multiplication agent (C) is very few, alkali will not efficiently be produced by alkali breeder reaction sometimes.When the amount of alkali multiplication agent (C) is excessive, alkali multiplication agent can be separated out sometimes.
(sensitising agent (D))
Due to containing above-mentioned Photobase generator (A) in the Photocurable composition of the present invention, even if without sensitising agent, the alkali of sufficient amount can also be produced in the case of short time and a small amount of irradiation light.But it is also possible to which Photobase generator (A) is applied in combination with sensitising agent (D).By the way that Photobase generator (A) and sensitising agent (D) is applied in combination, light decomposability can be further improved.
As above-mentioned sensitising agent (D), triple photo-excitation transfer sensitising agents or electro transfer sensitising agent etc. can be enumerated.As above-mentioned sensitising agent (D) specific example, it can enumerate for example：Acetophenones, benzophenone, Michler's keton, benzil, benzoin, benzoin ether, benzil dimethyl ketal, benzoylbenzoic acid ester, α-acyl oxime ester (α-acyloxime ester), tetramethylthiuram monosulfide, thioxanthones, aliphatic amine, amine containing aromatic group, the compound that the nitrogen such as piperidines exist as a part for ring, allylthiourea, o-tolyl thiocarbamide, diethyldithioposphoric acid sodium, the soluble salt of aromatic series sulfinic acid, N, N- bis- replaces to aminobenzonitrile class compound, tri-n-butyl phosphine, N- nitroso hydroxylamine derivatives, oxazole hydride compounds, tetrahydrochysene -1, 3- oxazine compounds, the condensation product of formaldehyde or acetaldehyde and diamines, anthracene, the derivative of anthracene, xanthine, N-phenylglycine, derivative of anthocyanin pigments corproporphyrin or anthocyanin pigments porphyrin etc..As above-mentioned anthocyanin pigments corproporphyrin, phthalocyanine, naphthalene cyanines or sulphur cyanines (thiocyanine) etc. can be enumerated.
Wherein, preferred thioxanthene ketone class sensitizer, because they can obtain extremely excellent light decomposability.It should be noted that so-called thioxanthene ketone class sensitizer, is thioxanthones or compound obtained from substituent has been imported in thioxanthones.As compound obtained from substituent has been imported in thioxanthones, it can enumerate for example：2,4- diethyl thioxanthones, CTX, 2,4- diisopropylthioxanthones, 2,4- dimethyl thioxanthones or isopropyl thioxanthone etc..
Relative to the above-mentioned Photobase generator of 100 parts by weight (A), above-mentioned sensitising agent (D) is contained preferably in the range of 1~100 parts by weight, above-mentioned sensitising agent (D) is contained more preferably in the range of 1~50 parts by weight.When the amount of sensitising agent (D) is very few, sufficiently sensitization effect can not be obtained sometimes.When the amount of sensitising agent (D) is excessive, the residue from sensitising agent (D) increases, and is difficult to obtain desired solidfied material sometimes.
(the other compositions that can be added)
The Photocurable composition of the present invention can also contain appropriate solvent.When Photocurable composition contains solvent, screening characteristics can be improved.
Above-mentioned solvent is not particularly limited.As the specific example of above-mentioned solvent, aromatic hydrocarbon compound, saturation or unsaturated hydrocarbon compound, ethers, ketone or esters etc. can be enumerated.These solvents can be used alone, and can also combine two or more and use.
As above-mentioned aromatic hydrocarbon compound, benzene, dimethylbenzene, toluene, ethylo benzene, styrene, trimethylbenzene or diethylbenzene etc. can be enumerated.As above-mentioned saturation or unsaturated hydrocarbon compound, hexamethylene, cyclohexene, cinene, pentane, isopentane, n-hexane, isohexane, normal heptane, isoheptane, normal octane, isooctane, n -nonane, isononane, n-decane, isodecane, tetrahydronaphthalene or three decanes etc. can be enumerated.It is used as above-mentioned ethers, ether can be enumerated, diη-propyl ether, Di Iso Propyl Ether, dibutyl ethers, ethyl propyl ether, diphenyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, diethylene glycol methyl ethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, DPG dibutyl ethers, dipropylene glycol methyl ethylether, ethylene glycol dimethyl ether, ethylene glycol Anaesthetie Ether, ethylene glycol dipropyl ether, Ethylene Glycol Methyl ethylether, tetrahydrofuran, 1, 4- dioxanes, propylene glycol monomethyl ether, ethylene glycol monoethylether acetate, dipropylene glycol methyl ether acetic acid esters, TC acetic acid esters, ethyl cyclohexane, hexahydrotoluene, it is right
Figure GPA00001022289300351
Alkane, neighbour
Figure GPA00001022289300352
Alkane,Alkane, dipropyl ether or dibutyl ethers etc..As above-mentioned ketone, acetone, MEK, methyl iso-butyl ketone (MIBK), metacetone, dipropyl ketone, methyl amyl ketone, cyclopentanone, cyclohexanone or cycloheptanone etc. can be enumerated.As above-mentioned esters, ethyl acetate, methyl acetate, butyl acetate, propyl acetate, cyclohexyl acetate, acetic acid methyl cellosolve, acetic cellosolve, acetic acid butyl cellosolve, ethyl lactate, propyl lactate, butyl lactate, isoamyl lactate or butyl stearate etc. can be enumerated.
In addition, as needed, other additives can also be added in Photocurable composition of the present invention.As additive, filler, pigment, dyestuff, levelling agent, defoamer, antistatic agent, ultra-violet absorber, pH adjusting agent, dispersant, dispersing aid, surface modifier, plasticizer, plasticising rush agent agent or anti-sagging agent etc. can be enumerated.
The manufacture method of the Photocurable composition of the present invention is not particularly limited.As the manufacture method of Photocurable composition, method can be listed below：The method that above-mentioned Photobase generator (A), above-mentioned curability compound (B) and each composition being added as needed on carry out melting mixing；Or the method by the dissolving of each composition in a solvent etc..
The light source that the Photocurable composition of the present invention is irradiated is not particularly limited.As light source, ultrahigh pressure mercury lamp, Deep UV lamps, high-pressure sodium lamp, low pressure mercury lamp, metal halide lamp, LED/light source or PRK etc. can be used.These light sources can suitably be selected according to the wavelength photoreceptor of composition contained in Photocurable composition, such as Photobase generator (A) or sensitising agent (D).
The irradiation energy of light can suitably be selected according to the species of composition contained in Photocurable composition, such as Photobase generator (A) or sensitizer (D).The irradiation energy of light is usually 10~2000mJ/cm2In the range of.The irradiation energy of light is less than 10mJ/cm2When, Photocurable composition will not fully solidify sometimes.The irradiation energy of light is more than 2000mJ/cm2When, irradiation time is long, makes solidfied material heat deterioration because of the infrared ray that light source is sent sometimes.
Photocurable composition can be applied on the matrix material with heat resistance, and solidifies Photocurable composition.Now, in order to promote solidification because of the amine produced irradiation light, Photocurable composition can be heated by heater.As above-mentioned heater, baking oven, heating gun, IR heaters, far-infrared heater, nichrome wire heater, medium heating device or induction heating device etc. can be enumerated.
For the Photocurable composition of the present invention, the quantum yield of the alkali produced by Photobase generator (A) is high, therefore, compared with using the situation of conventional Photobase generator (A), irradiation light energy can significantly be reduced, for example, can be by irradiation light Energy suppression 1/10th or so.
The Photocurable composition of the present invention is suitable as bonding agent, adhesive, coating, coating agent, sealant, resist, encapsulant or ink etc. and used.Wherein, Photocurable composition is used particularly preferable as bonding agent, coating agent.
Embodiment
Below, enumerate embodiment the present invention will be described in more detail.But the present invention is not limited in these embodiments.
(synthesis example 1)
The synthesis of Photobase generator (A1)
Using 20g Ketoprofens (ketoprofen) (carboxylic acid (a1) represented as above-mentioned formula (1)) (Tokyo HuaCheng Industry Co., Ltd's manufacture) and the 1 of 4.57g, 6- hexamethylenediamines (being used as alkali compounds (a2)) (Wako Pure Chemical Industries, Ltd.'s manufacture) are added in 50g methanol, it is stirred at room temperature 24 hours, is reacted it.Then, ethanol is removed by evaporator, then resulting thick product is recrystallized using ethanol/hexane, Photobase generator (A1) is obtained.
(synthesis example 2)
The synthesis of Photobase generator (A2)
Use 20g Ketoprofens (carboxylic acid (a1) represented as above-mentioned formula (1)) (Tokyo HuaCheng Industry Co., Ltd's manufacture) and the 1 of 8.2g, 3- bis- (4- piperidyls) propane (being used as alkali compounds (a2)) (Tokyo HuaCheng Industry Co., Ltd's manufacture), according to Photobase generator (A1) identical operation order, obtain Photobase generator (A2).
(synthesis example 3)
The synthesis of Photobase generator (A3)
Use 20g Ketoprofens (carboxylic acid (a1) represented as above-mentioned formula (1)) (Tokyo HuaCheng Industry Co., Ltd's manufacture) and 7.8g cyclohexylamine (being used as alkali compounds (a2)) (Wako Pure Chemical Industries, Ltd.'s manufacture), according to Photobase generator (A1) identical operation order, obtain Photobase generator (A3).
(synthesis example 4)
The synthesis of carbamyl imino group epoxide (カ Le バ モ イ Le イ ミ ノ オ キ シ) class compound
0.02 mole of hexamethylene diisocyanate and 0.04 mole of acetophenone oxime are dissolved in 50ml tetrahydrofurans (THF), stirred 5 hours in 60 DEG C under nitrogen atmosphere.Then, 5 hours are stood at room temperature, then obtained white crystals is collected by filtration.It is dried in vacuum drying chamber, THF is volatilized, obtains the carbamyl imino group epoxide class compound as the Photobase generator beyond Photobase generator (A).
(synthesis example 5)
The synthesis of compound (B2) containing NCO
Add polyether triol (ADEKA Corp.'s manufacture, trade name for the weight average molecular weight 4000 that 100 parts by weight are formed by trimethylolpropane and expoxy propane：ADEKA Polyether T-4000), 100 parts by weight PPOXs (weight average molecular weight 6000), diphenyl methane -4,4 '-diisocyanate (Japanese polyurethane Co., Ltd. manufacture, trade name：Millionate MT), and make NCO/OH ratios using equivalent ratio as 1.9, reacted 5 hours at 80 DEG C, obtain the compound (B2) (carbamate prepolymer) containing NCO as the curability compound at least with 2 NCOs.
(synthesis example 6)
The synthesis of compound (B4) containing alkoxysilyl
N-butyl acrylate (Japanese catalyst manufacture) 50g, ethyl acrylate (Japanese catalyst manufacture) 45g, 3- methyl allyl acyloxypropyl trimethoxysilane (KBM-503 of KCC of SHIN-ETSU HANTOTAI manufacture) 5g, dodecyl mercaptans (and the manufacture of Guang Chun medicines Co., Ltd.) 1g and toluene 100g are added in the 1L detachable flasks with mixer, cooler, thermometer and nitrogen inlet and is mixed, monomer mixture solution is obtained.Using nitrogen to obtained monomer mixture solution bubbling 20 minutes, dissolved oxygen is removed.Then, the temperature in detachable flask is heated up while stirring to entering line replacement in detachable flask system with nitrogen, until backflow.
Reach after backflow, with 1g toluene to 1,1-s bis- (tertiary hexyl peroxide) -3 of the 0.05g as polymerization initiator, 3,5- trimethyl-cyclohexanes are diluted and obtain solution, and the solution is added in polymerization system.After 1 hour, 1,1- bis- (tertiary hexyl peroxide) -3, solution obtained from 3,5- trimethyl-cyclohexanes are diluted to 0.1g with 1g toluene are added.And then 1,1- bis- (tertiary hexyl peroxide) -3, solution obtained from 3,5- trimethyl-cyclohexanes are diluted for using 1g toluene to 0.5g are added after polymerization starts 2 hours.Polymerization initiator is added for the first time after 4 hours, cooled down, 50g ethanol is added, the toluene/ethanol solution of the compound (B4) (number-average molecular weight of polystyrene conversion is about 9000) containing alkoxysilyl as the curability compound at least with 2 alkoxysilyls is obtained.
(synthesis example 7)
The synthesis of Photobase generator (A4)
Use 20g Ketoprofens (carboxylic acid (a1) represented as above-mentioned formula (1)) (Tokyo HuaCheng Industry Co., Ltd's manufacture) and 7.96g triethylamines (being used as alkali compounds (a2)) (Wako Pure Chemical Industries, Ltd.'s manufacture), according to the operation order same with Photobase generator (A1), Photobase generator (A4) is obtained.
(synthesis example 8)
The synthesis of Photobase generator (A5)
Use the 1 of 20g Ketoprofens (be used as above-mentioned formula (1) represent carboxylic acid (a1)) (Tokyo HuaCheng Industry Co., Ltd's manufacture) and 8.8g, 4- diazabicyclos [2.2.2] octane (being used as alkali compounds (a2)) (Tokyo HuaCheng Industry Co., Ltd's manufacture), according to the operation order same with Photobase generator (A1), Photobase generator (A5) is obtained.
(synthesis example 9)
The synthesis of Photobase generator (A6)
Use the 1 of 20g Ketoprofens (be used as above-mentioned formula (1) represent carboxylic acid (a1)) (Tokyo HuaCheng Industry Co., Ltd's manufacture) and 12g, 8- diazabicyclos [5.4.0] -7- hendecanes (DBU) (being used as alkali compounds (a2)) (Tokyo HuaCheng Industry Co., Ltd's manufacture), according to the operation order same with Photobase generator (A1), Photobase generator (A6) is obtained.
(synthesis example 10)
The synthesis of Photobase generator (A7)
Use 20g Ketoprofens (carboxylic acid (a1) represented as above-mentioned formula (1)) (Tokyo HuaCheng Industry Co., Ltd's manufacture) and 9g JEFFAMINE D-230 (being used as alkali compounds (a2)) (manufacture of Huntsman Co., Ltd.), according to the operation order same with Photobase generator (A1), Photobase generator (A7) is obtained.
(synthesis example 11)
The synthesis of Photobase generator (A8)
Use the 1 of 20g 2- phenylpropionic acids (be used as above-mentioned formula (1) represent carboxylic acid (a1)) (Tokyo HuaCheng Industry Co., Ltd's manufacture) and 14g, 3- bis- (4- piperidyls) propane (being used as alkali compounds (a2)) (Tokyo HuaCheng Industry Co., Ltd's manufacture), according to the operation order same with Photobase generator (A1), Photobase generator (A8) is obtained.
(synthesis example 12)
The synthesis of poly- (GMA/n-butyl acrylate) copolymer (B8)
50g n-butyl acrylates (Japanese catalyst manufacture), 50g GMAs (Mitsubishi Gas Chemical Co., Ltd's manufacture), 3g dodecyl mercaptans (and the manufacture of Guang Chun medicines Co., Ltd.) and 100g toluene are added in the 1L detachable flasks with mixer, cooler, thermometer and nitrogen inlet and is mixed, monomer mixture solution is obtained.Using nitrogen to obtained monomer mixture solution bubbling 20 minutes, dissolved oxygen is removed.Then, the temperature in detachable flask is heated up while stirring to entering line replacement in detachable flask system with nitrogen, until backflow.Then, it is polymerize according to the method same with synthesis example 6, obtain as the curability compound with least two glycidyl poly- (GMA/n-butyl acrylate) copolymer (B8) (polystyrene conversion number-average molecular weight be 3000, epoxide equivalent is toluene/ethanol solution 284).
(synthesis example 13)
The synthesis of poly- (GMA/n-butyl acrylate) copolymer (B9)
The addition of n-butyl acrylate (Japanese catalyst manufacture) is changed to 98.22g, the addition of GMA (Mitsubishi Gas Chemical Co., Ltd's manufacture) is changed to 1.78g, and the addition of dodecyl mercaptans (and Guang Chun medicines Co., Ltd. manufactures) is changed to 1.7g, in addition, according to the operation same with synthesis example 12, obtain as the curability compound with least two glycidyl poly- (GMA/n-butyl acrylate) copolymer (B9) (polystyrene conversion number-average molecular weight be 120000, epoxide equivalent is toluene/ethanol solution 8000).
(synthesis example 14)
The synthesis of poly- (GMA/n-butyl acrylate) copolymer (B10)
The addition of n-butyl acrylate (Japanese catalyst manufacture) is changed to 99.68g, the addition of GMA (Mitsubishi Gas Chemical Co., Ltd's manufacture) is changed to 0.32g, and the addition of dodecyl mercaptans (and Guang Chun medicines Co., Ltd. manufactures) is changed to 0.1g, in addition, according to the operation same with synthesis example 12, obtain as the curability compound with least two glycidyl poly- (GMA/n-butyl acrylate) copolymer (B10) (polystyrene conversion number-average molecular weight be 135000, epoxide equivalent is toluene/ethanol solution 45000).
(synthesis example 15)
The synthesis of poly- (GMA) (B11)
Without using n-butyl acrylate (Japanese catalyst manufacture), and the addition of GMA (Mitsubishi Gas Chemical Co., Ltd's manufacture) is changed to 100g, in addition, according to the operation same with synthesis example 12, the toluene/ethanol solution of poly- (GMA) (B11) (polystyrene conversion number-average molecular weight is 3000) as the curability compound with least two glycidyl is obtained.
(synthesis example 16)
The synthesis of poly- (GMA/n-butyl acrylate) copolymer (B12)
The addition of n-butyl acrylate (Japanese catalyst manufacture) is changed to 99.93g, the addition of GMA (Mitsubishi Gas Chemical Co., Ltd's manufacture) is changed to 0.07g, and dodecyl mercaptans (and Guang Chun medicines Co., Ltd. manufactures) is changed to 0.03g, in addition, according to the operation same with synthesis example 12, obtain as the curability compound with least two glycidyl poly- (GMA/n-butyl acrylate) copolymer (B12) (polystyrene conversion number-average molecular weight be 200000, epoxide equivalent is toluene/ethanol solution 66000).
(synthesis example 17)
The synthesis of HDI- fluorenemethanols addition product (C2)
In the reactor with mixer, cooler, thermometer and nitrogen inlet, add 40g and the toluene after diel is dried by molecular sieve 3a, 10g 9- fluorenemethanols (Tokyo HuaCheng Industry Co., Ltd's manufacture) are dissolved in the toluene, 4.28g 1,6- hexylidene diisocyanates are added dropwise (Tokyo is melted into Co., Ltd.'s manufacture).Then, stir 5 hours under nitrogen atmosphere, in 80 DEG C.Then, toluene is removed using evaporator, obtains the HDI- fluorenemethanols addition product (C2) as alkali multiplication agent.
(evaluation method of functional equivalent)
According to following evaluation method, the functional equivalent of the curability compound (B) used in embodiment and comparative example is obtained.As a result it is shown in table 1 below~3.Average functional equivalent is represented using functional equivalent during multiple curability compound (B).
When functional group is epoxy radicals, the method based on JIS K 7236 obtains curability compound (B) functional equivalent.
When functional group is (methyl) acryloyl group, the atomic weight (126.9) of iodine divided by the iodine number (mgI/g) obtained based on JIS K 0070, then multiplied by with 1000 times, thus obtain above-mentioned functional equivalent.
When functional group is NCO, thus the molecular weight (42.02) of NCO divided by based on the NCO containing ratio that JIS K7301 are obtained obtains above-mentioned functional equivalent.
When functional group is anhydride group, first, esterification is carried out using ethanol, at the same time, produce acid, be then based on JIS K 0070 and obtain acid number (mgKOH/g).KOH molecular weight 56.11 divided by the above-mentioned acid number obtained, then multiplied by with 1000 times, thus obtain above-mentioned functional equivalent.
When functional group is alkoxysilyl, the content (weight %) of contained silicon in the atomic weight 28 of silicon atom divided by the curability compound (B) for passing through determination of elemental analysis, then multiplied by with 1000 times, above-mentioned functional equivalent is thus obtained.
In the synthesis example for obtaining above-mentioned curability compound (B), when functional group does not consume in synthesis, above-mentioned functional equivalent is obtained according to following formulas by feed molar ratio.
Functional equivalent=(raw materials total amount)/∑ { (feeding quantity with the raw material n of functional group) × (functional group number with the raw material n of functional group)/(molecular weight with the raw material n of functional group) }
Wherein, (feeding quantity with the raw material n of functional group), (functional group number with the raw material n of functional group) and (molecular weight with the raw material n of functional group) represents the feeding quantity, functional group number and molecular weight equivalent to n raw material during the raw material for having functional group using n kinds respectively
∑ { (feeding quantity with the raw material n of functional group) × (functional group number with the raw material n of functional group)/(molecular weight with the raw material n of functional group) } is represented by obtaining the 1st kind of raw material (feeding quantity with the raw material n of functional group) × (functional group number with the raw material n of the functional group)/summation that is worth obtained from (molecular weight of the raw material n with functional group) to n with functional group.
Wherein, the raw material with functional group used is a kind, and when its functional group number is 1, by the deformation of above-mentioned formula, above-mentioned functional equivalent is expressed from the next.
Functional equivalent=100 × [number-average molecular weight with the raw material of functional group]/[feeding quantity (weight %) with the raw material of functional group]
(embodiment 1)
The above-mentioned Photobase generator of 60 parts by weight (A1) and 100 parts by weight ARONIX M8030 (Toagosei Co., Ltd manufactures) (being used as curability compound i.e. (methyl) acrylic resin (B1) at least with 2 (methyl) acryloyl groups) are diluted as diluent with 40 parts by weight of ethanol, Photocurable composition is obtained.
(embodiment 2)
The above-mentioned Photobase generator of 15 parts by weight (A1) and 100 parts by weight carbamate prepolymers (being the above-mentioned compound (B2) containing NCO as the above-mentioned curability compound with least two NCO) are diluted with 50 parts by weight of toluene, Photocurable composition is obtained.
(embodiment 3)
The above-mentioned Photobase generator of 130 parts by weight (A1) and 100 parts by weight RIKACID (リ カ シ Star De) MTA15 (being the compound (B3) containing anhydride group as the curability compound with least two anhydride group) (New Japan Chem Co., Ltd manufactures) are diluted as diluent with 100 parts by weight 1-METHYLPYRROLIDONEs, Photocurable composition is obtained.
(embodiment 4)
The toluene/ethanol solution of the resin (polystyrene conversion number-average molecular weight is about 9000) (being used as compound (B4) of the above-mentioned curability compound with least two alkoxysilyl i.e. containing alkoxysilyl) containing alkoxysilyl using the above-mentioned Photobase generator of 30 parts by weight (A1) and containing 100 parts by weight is mixed, and obtains Photocurable composition.
(embodiment 5)
The above-mentioned Photobase generator of 150 parts by weight (A1) and 100 parts by weight of bisphenol A type epoxy resin Epikote (ト of エ ピ Us one) 828 (Japanese epoxy resin Co., Ltd. manufactures) (being used as the curability compound i.e. epoxy resin (B5) with least two epoxy radicals) are diluted as diluent with 100 parts by weight of ethanol, Photocurable composition is obtained.
(embodiment 6)
The above-mentioned Photobase generator of 150 parts by weight (A1) and phenolic resin varnish type epoxy resin Epikote 152 (Japanese epoxy resin Co., Ltd. manufactures) (being used as the epoxy resin (B6) of the curability compound with least two epoxy radicals) are diluted as diluent with 100 parts by weight of ethanol, Photocurable composition is obtained.
(embodiment 7)
The above-mentioned Photobase generator of 150 parts by weight (A1) and 100 parts by weight glycidyl amine epoxy resin Epikote 1031S (Japanese epoxy resin Co., Ltd. manufactures) (being used as the curability compound i.e. epoxy resin (B7) with least two epoxy radicals) are diluted as diluent with 50 parts by weight of ethanol and 50 parts by weight of toluene, Photocurable composition is obtained.
(embodiment 8)
In addition to replacing above-mentioned Photobase generator (A1) with above-mentioned Photobase generator (A2), operate similarly to Example 5, obtain Photocurable composition.
(embodiment 9)
In addition to the above-mentioned Photobase generator of 20 parts by weight (A3) come instead of the above-mentioned Photobase generator of 150 parts by weight (A1), operate similarly to Example 5, obtain Photocurable composition.
(embodiment 10)
The compound Flu4 (C1) that the above-mentioned Photobase generator of 75 parts by weight (A1), 100 parts by weight of bisphenol A type epoxy resin Epikote828 (Japanese epoxy resin Co., Ltd. manufacture) (being epoxy resin (B5) as the curability compound with least two epoxy radicals) and 75 parts by weight are represented as the above-mentioned formula (14) of alkali multiplication agent is mixed, and thus obtains Photocurable composition.
(embodiment 11)
The above-mentioned Photobase generator of 150 parts by weight (A1), 100 parts by weight of bisphenol A type epoxy resin Epikote828 (Japanese epoxy resin Co., Ltd. manufacture) (being epoxy resin (B5) as the curability compound with least two epoxy radicals) and 5 parts by weight are mixed as the diethyl thioxanthone (D1) of sensitising agent, Photocurable composition is thus obtained.
(comparative example 1)
In addition to the carbamyl imino group epoxide class compound obtained except above-mentioned Photobase generator (A1) is substituted in synthesis example 4, operate similarly to Example 5, obtain Photocurable composition.
(embodiment 12~25)
In addition to being changed as described in Table 2 to the species and addition of Photobase generator (A) and curability compound (B), operate similarly to Example 1, obtain Photocurable composition.
(embodiment 26~30)
The species and addition to Photobase generator (A) and curability compound (B) are changed and the alkali multiplication agent (C) shown in Table 3 below are further added with the ratio shown in Table 3 below as described in Table 3, in addition, operate similarly to Example 1, obtain Photocurable composition.
(embodiment 31~37)
The species and addition to Photobase generator (A) and curability compound (B) are changed and the sensitising agent (D) shown in Table 3 below are further added with the ratio shown in table 3 as described in Table 3, in addition, operate similarly to Example 1, obtain Photocurable composition.
(comparative example 2)
The above-mentioned Photobase generator of 60 parts by weight (A1) is substituted for the above-mentioned Photobase generator of 20 parts by weight (A6) and (methyl) acrylic resin (B1) of 100 parts by weight as curability compound is substituted for 100 parts by weight polyimide precursors (RIKACOAT SN-20, New Japan Chem Co., Ltd's manufacture), in addition, operate similarly to Example 1, obtain Photocurable composition.
(evaluation)
(1) except sticky (tack free) irradiation energy
Obtained each Photocurable composition is coated with a glass, and makes dried thickness be about 50 μm, is dried 15 minutes in 120 DEG C of baking ovens, diluent is volatilized, obtain the film of Photocurable composition.Irradiate 365nm light to obtained film from top with high-pressure sodium lamp, its illumination is 5mw/cm2.Determine from the time for starting irradiation light when film is contacted with finger untill imperceptible viscosity, irradiation energy is calculated in the product by illumination and irradiation time.
(2) shear bond power and peeling adhesion force
Based on JIS Z6850, the surface degreaser drying of long 150mm × wide 30mm × thickness 2mm acrylic panel is made with ethanol, Photocurable composition is then coated with the surface of the acrylic panel, and make its thickness be 50 μm.Photocurable composition on acrylic panel is dried 15 minutes in 120 DEG C of baking oven, diluent is volatilized.Then, the sour plate of the one piece of aforesaid propylene preparing in addition of being fitted on Photocurable composition, obtains conjugant.Then, in 300~370nm wavelength region, with composition surface irradiation light of the light of 365nm wavelength to above-mentioned conjugant so that irradiate light quantity reaches intensity 10mW/cm2And irradiation time is 60 seconds.
After irradiation light, the failure by shear intensity and stripping damage intensity of above-mentioned conjugant are determined under conditions of draw speed 10mm/ divides using cupping machine.Determine after bond area, obtained failure by shear intensity divided by bond area obtains shear bond power.The size that position is peeled off in the direction of the width is peeled off in addition, obtaining, stripping damage intensity divided by the size peeled off in the direction of the width obtain peeling adhesion force.
The sour plate of aforesaid propylene is replaced using glass plate (long 150mm × wide 30mm × thickness 8mm), same experiment is carried out.
(3) the プ Try test of gridiron pattern tape test (Ji Disk mesh テ mono-)
Photocurable composition obtained above is coated with the acrylic panel for having carried out degreaser drying processing to surface with ethanol, and makes dried film thickness be 50 μm.Photocurable composition on acrylic panel is dried 15 minutes in 120 DEG C of baking oven, diluent is volatilized, obtains the film of Photocurable composition.Using high-pressure sodium lamp from obtained film top with intensity 10mw/cm2Condition to film irradiate 365nm light, irradiation time be 60 seconds.Then, gridiron pattern tape test, records appraisal points are carried out based on JIS K 5400.It should be noted that evaluating, points are higher, and expression film is higher to the adaptation of acrylic panel.
As a result it is shown in table 1 below~3.
Figure GPA00001022289300461
Figure GPA00001022289300471
Figure GPA00001022289300481

Claims (13)

1. a kind of Photocurable composition, it contains Photobase generator (A) and curability compound (B),
The Photobase generator (A) is the salt that the carboxylic acid (a1-1) and alkali compounds (a2) represented by following formula (1-1) is formed；Also,
In the curability compound (B), a molecule at least has 2 functional groups selected from epoxy radicals, (methyl) acryloyl group, NCO, anhydride group and alkoxysilyl；
Figure FPA00001022289200011
In above-mentioned formula (1-1), R1~R7 represents hydrogen or organic group respectively, and R1~R7 is identical or different, and 2 in R1~R7 are optionally mutually bonded and form cyclic structure.
2. Photocurable composition according to claim 1, wherein, 1 in R3~R7 in above-mentioned formula (1-1) is the organic group that following formula (1-2) is represented,
Figure FPA00001022289200012
In above-mentioned formula (1-2), R8~R12 represents hydrogen or organic group respectively, and R8~R12 is identical or different, and 2 in R8~R12 are optionally mutually bonded and form cyclic structure.
3. Photocurable composition according to claim 1 or 2, wherein, the R1 in above-mentioned formula (1-1) is methyl.
4. according to Photocurable composition according to any one of claims 1 to 3, wherein, the carboxylic acid (a1-1) that above-mentioned formula (1-1) represents is the carboxylic acid (a1) that following formula (1) is represented,
Figure FPA00001022289200013
5. according to Photocurable composition according to any one of claims 1 to 4, wherein, the curability compound (B) is the curability compound at least in a molecule with 2 epoxy radicals, and at least one kind of in glycidyl ether type epoxy resin, glycidyl ester epoxy resin and glycidyl amine epoxy resin.
6. according to Photocurable composition according to any one of claims 1 to 4, wherein, the curability compound (B) is the carbamate prepolymer with NCO.
7. according to Photocurable composition according to any one of claims 1 to 6, wherein, the alkali compounds (a2) is amine.
8. Photocurable composition according to claim 7, wherein, in amine described in a molecule, with least two amino.
9. Photocurable composition according to claim 7, wherein, the amine is the amine represented by any one chemical formula in following formula (2)~(7),
Figure FPA00001022289200021
(CH3)4N+OH-(4),
Figure FPA00001022289200022
In above-mentioned formula (5), R1The alkylidene that carbon number is 1~10 is represented,
H2N-R2-NH2    (6)
In above-mentioned formula (6), R2The alkylidene that carbon number is 1~10 is represented,
Figure FPA00001022289200023
10. according to Photocurable composition according to any one of claims 1 to 9, wherein, also containing alkali multiplication agent (C).
11. according to Photocurable composition according to any one of claims 1 to 10, wherein, also containing sensitising agent (D).
12. the Photocurable composition according to any one of claim 1~11; wherein, the mol ratio of the basic functionality of the functional group being selected from epoxy radicals, (methyl) acryloyl group, NCO, anhydride group and alkoxysilyl and the alkali compounds (a2) is in the range of 1: 0.01~1: 2.
13. the Photocurable composition according to any one of claim 1~12; wherein, the number-average molecular weight of the curability compound (B) divided by the number of value, the i.e. number-average molecular weight/functional group obtained from epoxy radicals, (methyl) acryloyl group, NCO, anhydride group and the number of the functional group in alkoxysilyl are in the range of 170~50000.
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